Tear resistant adherent gels, composites, and articles

ABSTRACT

Adherent gels and adherent gel composites which can be made by applying a tear resistant adherent gel of SEEPS onto one or more selected substrates of foam, plastic, fabric, metal, concrete, wood, wire screen, refractory material, glass, synthetic resin, synthetic fibers, and the like. Such adherent gels and gel composites are useful for protecting articles, the body and skin.

RELATED APPLICATIONS

This application is a continuation-in-part of the followingapplications: Ser. No. 09/896,047 filed Jun. 30, 2001; Ser. No.10/273,828 filed Oct. 17, 2002 now U.S. Pat. No. 6,909,220; Ser. No.10/334,542 filed Dec. 31, 2002; Ser. No. 10/299,073 filed Nov. 18, 2002;Ser. No. 10/199,364 filed Jul. 20, 2002 now U.S. Pat. No. 6,794,440;Ser. No. 09/721,213 filed Nov. 21, 2000 now U.S. Pat. No. 6,867,253;Ser. No. 10/199,361 filed Jul. 20, 2002; Ser. No. 10/199,362 filed Jul.20, 2002; Ser. No. 10/199,363 filed Jul. 20, 2002; Ser. No. 09/517,230,filed Mar. 2, 2000 now abandoned; Ser. No. 09/412,886, filed Oct. 5,1999 now abandoned; Ser. No. 09/285,809, filed Apr. 1, 1999 nowabandoned; Ser. No. 09/274,498, filed Mar. 28, 1999 now U.S. Pat. No.6,420,475; Ser. No. 08/130,545, filed Oct. 1, 1993 now U.S. Pat. No.5,467,626; Ser. No. 08/984,459, filed Dec. 3, 1997 now U.S. Pat. No.6,324,703; Ser. No. 08/909,487, filed Aug. 12, 1997 now U.S. Pat. No.6,050,871; Ser. No. 08/863,794, filed May 27, 1997 now U.S. Pat. No.6,117,176; PCT/US97/17534, filed 30 Sep. 1997; U.S. Ser. No. 08/719,817filed Sep. 30, 1996 now U.S. Pat. No. 6,148,830; U.S. Ser. No.08/665,343 filed Jun. 17, 1996 which is a Continuation-in-part of U.S.Ser. No. 08/612,586 filed Mar. 8, 1996 (now U.S. Pat. No. 6,552,109);PCT/US94/04278 filed Apr. 19, 1994 (published May 26, 1995 No.WO95/13851); PCT/US94/07314 filed Jun. 27, 1994 (published Jan. 4, 1996No. WO 96/00118); Ser. No. 08/288,690 filed Aug. 11, 1994 now U.S. Pat.No. 5,633,286; Ser. No. 08/581,188 filed Dec. 29, 1995 now abandoned;Ser. No. 08/581,191 filed Dec. 29, 1995; Ser. No. 08/581,125 filed Dec.29, 1995 now U.S. Pat. No. 5,962,527. In turn U.S. Ser. Nos. 08/581,188;08/581,191; and 08/581,125 (now U.S. Pat. No. 5,962,572) arecontinuation-in-parts of the following applications: Ser. No.08/288,690, filed Aug. 11, 1994, PCT/US94/07314 filed Jun. 27, 1994 (CIPof PCT/US 94/04278, filed 19 Apr. 1994). The subject matter contained inthe related applications and patents are specifically incorporatedherein by reference.

FIELD OF THE INVENTION

The present invention is directed to novel gels and their uses.

BACKGROUND OF THE INVENTION

This application is base upon subject matters described in earlier filedand copending related applications and patents (see Related Applicationsabove) which are specifically incorporated herein by reference.

SUMMARY OF THE INVENTION

I have now discovered novel gels with improved properties made fromsubstantially random copolymers (pseudo-random copolymers orinterpolymers) having polyethylene segments which can be crystallizable.The invention gels advantageously exhibit improved properties over gelsmade without such substantially random copolymers. The invention gelsexhibit one or more property improvements, such as, higher tearresistances, greater fatigue resistance, increased tensile strength,improved damage tolerance, improved crack propagation resistance,improved resistance to high stress rupture, etc. Such improve gels areadvantageous for end-use involving repeated applications of stress andstrain resulting from large number of cycles of deformations, includingcompression, compression-extension (elongation), torsion,torsion-compression, torsion-elongation, tension, tension-compression,tension-torsion, and the like. Such improved properties makes thepresent invention gels advantageously and surprisingly exceptionallymore suitable than gels of corresponding gel rigidities made fromamorphous block copolymers such aspoly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-propylene-styrene), high vinylpoly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-ethylene-butylene-styrene) alone.

An embodiment of the gel compositions and s of the invention comprises:

(I) 100 parts by weight of

(i) one or more poly(ethylene-styrene), interpolymers produced bymetallocene catalysts, having one or more glassy components and at leastone crystalizable polyethylene components, wherein said (i) copolymersbeing in combination with a selected amount of one or more selectedsecond copolymers comprising:

(ii) one or more poly(ethylene-styrene), interpolymers, produced bymetallocene catalysts, having one or more glassy components and one ormore crystalizable polyethylene components of moderate crystallinity;

(iii) one or more poly(ethylene-styrene), interpolymers, produced bymetallocene catalysts, having one or more glassy components and one ormore crystalizable polyethylene components of low crystallinity,

(iv) one or more poly(ethylene-styrene), interpolymers, produced bymetallocene catalysts, having one or more glassy components and one ormore amorphous polyethylene components;

(v) one or more of a diblock, triblock, multi-arm block, branched block,radial block, or multiblock copolymers, wherein said (v) copolymershaving one or more glassy components and one or more elastomericcomponents having polyethylene segments which can be crystallizable asto exhibit a crystallization exotherm by DSC curve; and

(vi) one or more of a diblock, triblock, multi-arm block, branchedblock, radial block, or multiblock copolymers, wherein said (vi)copolymers having one or more glassy components and one or moreamorphous elastomeric components;

(vii) a mixture of two or more (ii)–(vi) copolymers;

wherein said (i), (ii), and (iii) copolymers having polyethylenesegments which can be crystallizable as to exhibit a crystallizationexotherm by DSC curve,

(II) in combination with or without one or more of selected polymers orcopolymers,

(III) a selected amount of one or more compatible plasticizers ofsufficient amounts to achieve a stable gel having rigidities of fromless than about 2 gram Bloom to about 1,800 gram Bloom; and incombination with or without

(IV) a selected amount of at least one adhesion resins.

A further embodiment of the invention comprises: a gel compositioncomprising:

(i) 100 parts by weight of one or a mixture of two or more of ahydrogenated styrene isoprene/butadiene block copolymer(s), wherein said(i) block copolymers have the formulapoly(styrene-ethylene-ethylene-propylene-styrene); from

(ii) about 300 to about 1,600 parts by weight of a plasticizing oil;said gel composition characterized by a gel rigidity of from about 20 toabout 1,800 gram Bloom; and in combination with or without

(iii) a selected amount of one or more polymers or copolymers ofpoly(styrene-butadiene-styrene), poly(styrene-butadiene)_(n),poly(styrene-isoprene-styrene)_(n), poly(styrene-isoprene)_(n),poly(styrene-ethylene-propylene),poly(styrene-ethylene-propylene-styrene),poly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-butylene), poly(styrene-ethylene propylene)_(n),poly(styrene-ethylene-butylene)_(n), polystyrene, polybutylene,poly(ethylene-propylene), poly(ethylene-butylene), polypropylene, orpolyethylene, wherein said selected copolymer is a linear, radial,star-shaped, branched or multiarm copolymer, wherein n is greater thanone; and in combination with or without

(iv) a selected amount of one or more glassy component associatingresins having softening points above about 120° C.

Another embodiment of the invention comprises: a gel compositioncomprising:

(i) 100 parts by weight of one or morepoly(styrene-ethylene-ethylene-propylene-styrene) block copolymer(s);from

(ii) about 300 to about 1,600 parts by weight of a plasticizing oil;said gel composition characterized by a gel rigidity of from about 20 toabout 800 gram Bloom; and in combination with

(iii) a selected amount of one or more block copolymers ofpoly(styrene-butadiene-styrene), poly(styrene-butadiene)_(n), andpoly(styrene-ethylene-butylene-styrene), wherein said selected copolymeris a linear, radial, star-shaped, branched or multiarm copolymer,wherein n is greater than one.

A further embodiment of the invention comprises: a gel compositioncomprising:

(i) 100 parts by weight of one or morepoly(styrene-ethylene-ethylene-propylene-styrene) block copolymer(s);

(iii) a selected amount of one or more block copolymers ofpoly(styrene-butadiene-styrene), poly(styrene-butadiene)_(n),poly(styrene-ethylene-propylene-styrene), andpoly(styrene-ethylene-butylene-styrene), wherein said selected copolymeris a linear, radial, star-shaped, branched or multiarm copolymer,wherein n is greater than one;

(ii) about 300 to about 1,600 parts by weight of a plasticizing oil;said gel composition characterized by a gel rigidity of from about 20 toabout 800 gram Bloom; and in combination with or without

(iv) a selected amount of at least one adhesion resins.

Still another embodiment of the invention comprises: an adherent gelcomposition comprising:

(i) 100 parts by weight of one or a mixture of two or more of ahydrogenated styrene isoprene/butadiene block copolymer(s), wherein said(i) block copolymers have the formulapoly(styrene-ethylene-butylene-styrene); from

(ii) about 300 to about 1,600 parts by weight of a plasticizing oil;said gel composition characterized by a gel rigidity of from about 20 toabout 800 gram Bloom; and in combination with or without

(iii) a selected amount of one or more polymers or copolymers ofpoly(styrene-butadiene-styrene), poly(styrene-butadiene)_(n),poly(styrene-isoprene-styrene)_(n), poly(styrene-isoprene)_(n),poly(styrene-ethylene-propylene),poly(styrene-ethylene-propylene-styrene), low viscositypoly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-butylene), poly(styrene-ethylene propylene)_(n),poly(styrene-ethylene-butylene)_(n), polystyrene, polybutylene,poly(ethylene-propylene), poly(ethylene-butylene), polypropylene, orpolyethylene, wherein said selected copolymer is a linear, radial,star-shaped, branched or multiarm copolymer, wherein n is greater thanone; and in combination with

(iv) a minor amount of at least one or more adhesion resins.

As used herein, the term “gel rigidity” in gram Bloom is determined bythe gram weight required to depress a gel a distance of 4 mm with apiston having a cross-sectional area of 1 square centimeter at 23° C.

The various aspects and advantages will become apparent to those skilledin the art upon consideration of the accompanying disclosure.

DESCRIPTION OF THE DRAWINGS

FIG. 1. Representative sectional view of gel, and gel articles.

FIGS. 2 a–2 d. Representative sectional view of gel, and gel articles.

FIGS. 3 a–3 n. Representative sectional view of gel, and gel articles.

FIGS. 4 a–4 w. Representative sectional view of gel, and gel articles.

DESCRIPTION OF THE INVENTION

A internet search of the USPTO Patent Data Base of Applicant's publishedpatent applications and issued patent describing gel compositions usefulfor fishing identified: 20020188057; U.S. Pat. Nos. 6,420,475,6,161,555, 6,333,374; 6,324,703; 6,148,830; 6,117,176; 6,050,871;6,033,283, 5,962,572, 5,938,499, 5,884,639, 8597, 5,760,117, 5,655,947,5,633,286, 5,508,334, 5,624,294, 5,508,334, 5,475,890, 5,336,708,5,334,646; 5,324,222, 5,329,723, 5,262,468, 5,153,254, PCT/US97/17534,PCT/US94/04278 and PCT/US94/0731 which are incorporated herein byreference.

Block and other copolymers are described in the following publications:

(1) W. P. Gergen, “Uniqueness of Hydrogenated Block Copolymers forElastomeric Applications,” presented at the German Rubber Meeting,Wiesbaden, 1983; Kautsch, Gummi, Kunstst. 37, 284 (1984). (2) W. P.Gergen, et al., “Hydrogenated Block Copolymers,” Paper No. 57, presentedat a meeting of the Rubber Division ACS, Los Angeles, Apr. 25, 1985.Encyclopedia of Polymer Science and Engineering, Vol. 2, pp 324–434,“Block Copolymers”. (3) L. Zotteri and et al., “Effect of hydrogenationon the elastic properties of poly(styrene-b-diene-b-styrene)copolymers”, Polymer, 1978, Vol. 19, April. (4) J. Kenneth Craver, etal., Applied Polymer Science, Ch. 29, “Chemistry and Technology of BlockPolymers”, pp. 394–429, 1975. (5) Y. Mahajer and et al., “The influenceof Molecular Geometry on the Mechanical Properties of homopolymers andBlock Polymers of Hydrogenated Butadiene and Isoprene” reported underU.S. ARO Grant No. DAAG29-78-G-0201. (6) J. E. McGrath, et al., “Linearand Star Branched Butadiene-Isoprene Block Copolymers and TheirHydrogenated Derivatives”, Chem. Dept, Virginia Polytechnic Instituteand State University Blacksturg, Va., reported work supported by ArmyResearch Office. (7) Legge, Norman R., “Thermoplastic Elastomers”,Charles Goodyear Medal address given at the 131st Meeting of the RubberDivision, American Chemical Society, Montreal, Quebec, Canada, Vol. 60,G79–G115, May 26–29, 1987. (8) Falk, John Carl, and et al., “Synthesisand Properties of Ethylene-Butylene-1 Block Copolymers”, Macromolecules,Vol. 4, No. 2, pp. 152–154, March–April 1971. (9) Morton, Maurice, andet al., “Elastomeric Polydiene ABA Triblock Copolymers withinCrystalline End Blocks”, University of Arkon, work supported by GrantNo. DMR78-09024 from the National Science Foundation and ShellDevelopment Co. (10) Yee, A. F., and et al., “Modification of PS byS-EB-S Block Copolymers: Effect of Block Length”, General ElectricCorporate Research & Development, Schenectady, N.Y. 12301. (11)Siegfried, D. L., and et al., “Thermoplastic Interpenetrating PolymerNetworks of a Triblock Copolymer elastomer and an Ionomeric PlasticMechanical Behavior”, Polymer Engineering and Science, January 1981,Vol. 21, No. 1, pp 39–46. (12) Clair, D. J., “S-EB-S Copolymers ExhibitImproved Wax Compatibility”, Adhesives Age, November, 1988. (13) ShellChemical Technical Bulletin SC: 1102–89, “Kraton® Thermoplastic Rubbersin oil gels”, April 1989. (14) Chung P. Park and George P. Clingerman,“Compatibilization of Polyethylene-Polystyrene Blends withEthylene-Styrene Random Copolymers”, the Dow Chemical Company, May 1996.(15) Steve Hoenig, Bob Turley and Bill Van Volkenburgh, “MaterialProperties and Applications of Ethylene-Styrene Interpolymers”, the DowChemical Company. September 1996. (16) Y. Wilson Cheung and Martin J.Guest, “Structure, Thermal Transitions and Mechanical Properties ofEthylene/Styrene Copolymers”, the Dow Chemical Company, May 1996. (17)Teresa Plumley Karjaia, Y. Wilson Cheung and Martin J. Guest, “MeltRheology and Processability of Ethylene/Styrene Interpolymers”, the DowChemical Company, May 1997. (18) D. C. Prevorsek, et al., “Origins ofDamage Tolerance in Ultrastrong Polyethylene Fibers and s:, Journal ofPolymer Science: Polymer Symposia No. 75, 81–104 (1993). (19) Chen, H.,et al, “Classification of Ethylene-Styrene Interpolymers Based onComonomer Content”, J. Appl. Polym. Sci., 1998, 70, 109. (20–24) U.S.Pat. Nos. 5,872,201; 5,460,818; 5,244,996; EP 415815A; JP07,278,230describes substantially random, more appropriately presudo-randomcopolymers (interpolymers), methods of making and their uses. (25)Alizadeh, et al., “Effect of Topological Constraints on TheCrystallization Behavior of Ethylene/alp[ha-Olefin Copolymers”. PMSE,Vol, 81, pp. 248–249, Aug. 22–26, 1999. (26) Guest, et al.,“Structure/Property Relationships of Semi-Crystalline Ethylene-StyreneInterpolymers (ESI)”, PMSE, Vol, 81, pp. 371–372, Aug. 22–26, 1999. (27)A. Weill and R. Pixa, in Journal of Polymer Science Symposium, 58,381–394 (1977), titled: “Styrene-diene Triblock Copolymers: OrientationConditions and Mechanical Properties of the Oriented Materials” describetechniques of orientation of neat SIS and SBS block copolymers and theirproperties. (28) Elastomeric Thermoplastic, Vol. 5, pages 416–430; BlockCopolymers, Vol. 2, pages 324; Block and Graft Copolymers; Styrene-DieneBlock Copolymers, Vol. 15, pages 508–530; and Microphase Structure, canbe found in ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING, 1987. (29)Legge, N. R. et al., Chemistry and Technology of Block Polymers, Ch. 29,pages 394–429, ACS, Organic Coatings and Plastics Chemistry,© 1975. (30)Legge, N. R., Thermoplastic Elastomers, Rubber Chemistry and Technology,Vol. 60, pages G79–117. (31) Lindsay, G. A., et al., Morphology of LowDensity Polyethylene/EPDM Blends Having Tensile Strength Synergism,source: unknown. (32) Cowie, J. M. G., et al., Effect of Casting on theStress-Hardening and Stress-Softening Characteristics of Kraton-G 1650Copolymer Films, J. Macromol. Sci.-Phys., B16(4), 611–632 (1979). (33)Futamura, S., et al., Effects of Center Block Structure on the Physicaland Rheological Properties of ABA Block Copolymers. Part II. RheologicalProperties, Polymer Engineering and Science, August, 1977, Vol. 17, No.8, pages 563–569. (34) Kuraray Co., LTD. MSDS, Kuraray Septon 4055,Hydrogenated Styrene Isoprene/Butadiene Block Copolymer, Apr. 25, 1991.(35) Hoening, et al. U.S. Pat. No. 6,156,842, 23, May 2000, “Structuresand fabricated articles having shape memory made from Alpha-olefin/vinylor vinylidene aromatic and/or hindered aliphatic vinyl or vinylideneinterpolymers. (36) Shell Technical bulletin SC: 1102–89 “Kraton®Thermoplastic Rubbers in oil gels”, April 1989. (37) Witco productsliterature #19610M 700-360: “White oils Petrolatum, MicrocrystallineWaxes, Petroleum Distillates”, 1996 Witco Corporation. (38) Witcopresentation: “White Mineral Oils in Thermoplastic Elastomers”, ANTEC2002, May 5–8, 2002. (39) Lyondell literature LPC-8126 January 1993,“Product Descriptions of White Mineral Oils”, pp 30–33. (40) Collins,Jr., Henry Hill, “COMPLETE FIELD GUIDE TO AMERICAN WILDLIFE”, 1959,LCCN: 58-8880. (41) Romanack, Mark, Bassin' with the Pros, 2001, LCCN:2001086512. (42) Salamone, Joseph C., Concise Polymeric MaterialsEncyclopedia, CRC Press, 1999. (43) Lide, David R., Handbook ofChemistry and Physics, CRC Press, 78th Edition, 1997–1998. (44) Sigmayear 2002–2003 Biochemical and Reagents for life Science Research,sigma-aldrich.com. (45) Kraton Polymers and Compounds, TypicalProperties Guide. K0137 Brc-00U, 2001. (46) Kraton Thermoplastic Rubber,Typical properties 1988, SC: 68–78, May 1988 5M. (47) Humko chemicalProduct Guide, Witco 1988. (48) Opportunities with Humko chemicalKemamide fatty amides, Witco 1987. The above applications, patents andpublications are specifically incorporated herein by reference. (49) J.C. Randall, “A Review of High Resolution Liquid 13Carbon NuclearMagnetic Resonance Characterizations of Ethylene-Based Polymers”JMS—Review Macromol. Chem. Phys. C29 (2 & 3), 201–317 (1989). (50)Silipos product catalogue Page 7 for Single Sock Gel Liner (with respectto Product sales dates: #1272 on or about Jan. 31, 1995, #1275 on orabout Jan. 31, 1995, and #1276 same as #1272 but a different size on orabout Dec. 31, 1994). (51) “SiloLiner” Sales literature from Knit-Ritemedical (Mar. 1, 1999 3 pp.). (52) ALPS South Corporation—Gel Liners:NEW! Easy Liner ELPX, ELDT and ELFR published fact sheet on the Interneton Aug. 10, 1999.

Legge's paper teaches the development of (conventional substantiallyamorphous elastomer mid segment) SEBS triblock copolymers. In thepolymerization of butadiene by alkylithium initiators, 1,4-addition or1,2-addition polymers, mixtures, can be obtained. In forming styrenebutadiene triblock copolymers involving the addition of solvating agentssuch as ethers just before the final styrene charge is added, any excessof ethers can alter the polybutadiene structure from a 1,4-cis or transstructure to a 1,2- or 3,4-addition polymer. Using difunctional couplingagent would give linear block copolymers and multifunctional agentswould give star-shaped or radial block copolymers. Hydrogenation of the1,4-polybutadiene structure yields polyethylene, while that of the1,2-polybutadiene yields polybutylene. The resulting polyethylene willbe essentially identical with linear, high-density polyethylene with amelting point, Tm, of about 136° C. Hydrogenation of 1,2-polybutadienewould yield atactic poly(1-butene) (polybutylene). The Tg ofpolybutylene is around −18° C. Random mixtures of ethylene and butyleneunits in the chain would suppress crystallinity arising frompolyethylene sequences. The objective for a good elastomer should be toobtain a saturated olefin elastomeric segment with the lowest possibleTg and the best elastomeric properties. Such an elastomer favored usingstyrene as the hard-block monomer and selecting the best monomer forhydrogenation of the elastomer mid segment. Using a mixture of 1,4- and1,2-polybutadiene as the base polymer for the mid segment would resultin an ethylene/butylene mid segment in the final product. The elementsof selection of the midsegment composition is elastomer crystallinityand the elastomer Tg of an ethylene/butylene copolymer. Very low levelsof crystallinity can be achieved around 40–50% butylene concentration.The minimum in dynamic hysteresis around 35% butylene concentration inthe elastomeric copolymer. A value of 40% butylene concentration in theethylene/butylene midsegment was chosen for the S-EB-S block copolymers.Clair's paper teaches that the EB midblock of conventional S-EB-Spolymers is a random copolymer of ethylene and 1-butene exhibitingnearly no crystallinity in the midblock. In the preparation ofethylene-butylene (EB) copolymers, the relative proportions of ethyleneand butylene in the EB copolymer chain can be controlled over a broadrange from almost all ethylene to almost all butylene. When the EBcopolymer is nearly all ethylene, the methylene sequences willcrystallize exhibiting properties similar to low density polyethylene.In differential scanning calorimeter (DSC) curves, the melting endothermis seen on heating and a sharp crystallization exotherm is seen oncooling. As the amount of butylene in the EB copolymer is increased, themethylene sequences are interrupted by the ethyl side chains whichshorten the methylene sequences length so as to reduce the amount ofcrystallinity in the EB copolymer. In conventional S-EB-S polymers, theamount of 1-butene is controlled at a high enough level to make the EBcopolymer midblock almost totally amorphous so as to make the copolymerrubbery and soluble in hydrocarbon solvents. Clair suggests that anS-EB-S polymer retaining at least some crystallinity in the EB copolymermidblock may be desirable. Therefore, a new family of S-EB-S polymersare developed (U.S. Pat. No. 3,772,234) in which the midblock contains ahigher percentage of ethylene. The molecular weights of the newcrystalline midblock segment S-EB-S polymers can vary from low molecularweight, intermediate molecular, to high molecular weight; these aredesignated Shell GR-3, GR-1, and GR-2 respectively. Unexpectly, thehighest molecular weight polymer, GR-2 exhibits an anomalously lowsoftening point. A broad melting endotherm is seen in the DSC curves ofthese polymers. The maximum in this broad endotherm occurs at about 40°C. Himes, et al., (U.S. Pat. No. 4,880,878) describes SEBS blends withimproved resistance to oil absorption. Papers (14)–(17) describespoly(ethylene-styrene) substantially random copolymers (DowInterpolymers™): Dow S, M and E Series produced by metallocenecatalysts, using single site, constrained geometry additionpolymerization catalysts resulting in poly(ethylene-styrene)substantially random copolymers with weight average molecular weight(Mw) typically in the range of 1×10⁵ to 4×10⁵, and molecular weightdistributions (Mw/Mn) in the range of 2 to 5. Paper (18) Prevorsek, etal., using Raman spectroscopy, WAXS, SAXD, and EM analysis interpretsdamage tolerance of ultrastrong PE fibers attributed to the nano scalestructure that consists of needle-like-nearly perfect crystals that arecovalently bonded to a rubbery matrix with a structure remarkablysimilar to the structure of NACRE of abalone shells which explains thedamage tolerance and impact resistance of PE fibers. PE because of itsunique small repeating unit, chain flexibility, ability to undergo solidstate transformation of the crystalline phase without breaking primarybonds, and its low glass transition temperature which are responsiblefor large strain rate effects plays a key role in the damage toleranceand fatigue resistance of structures made of PE fibers. Chen (19)classifies 3 distinct categories of E (approximately 20–50 wt %styrene), M (approximately 50–70 wt % styrene), & S (greater thanapproximately 70 wt % styrene) substantially random or moreappropriately pseudo-random ethylene-styrene copolymers or randomcopolymers of ethylene and ethylene-styrene dyads. The designatedEthylene-styrene copolymers are: E copolymers (ES16, ES24, ES27, ES28,ES28, ES30, and ES44 with styrene wt % of 15.7, 23.7, 27.3, 28.1, 39.6 &43.9 respectively), M copolymers (ES53, ES58, ES62, ES63, and ES69 withstyrene wt % of 52.5, 58.1, 62.7, 62.8, and 69.2 respectively andcrystallinity, %, DSC, based on copolymer of 37.5, 26.6, 17.4, 22.9,19.6 and 5.0 respectively), S copolymers (ES72, ES73, and ES74 withstyrene wt % of 72.7, 72.8, and 74.3 respectively). The maximumcomonomer content for crystallization of about 20% is similar in otherethylene copolymers, such as in ethylene-hexene and ethylene-vinylacetate copolymers. If the comonomer can enter the crystal lattice, suchas in ethylene-propylene, compositions in excess of 20 mol % comonomercan exhibit crystallinity. The molecular weight distribution of thesecopolymers is narrow, and the comonomer distribution is homogeneous.These copolymers exhibit high crystalline, lamellar morphologies tofringed micellar morphologies of low crystallinity. Crystallinity isdetermined by DSC measurements using a Rheometric DSC. Specimensweighing between 5 and 10 mg are heated from −80 to 180° C. at a rate of10° C./min (first heating), held at 190° C. for 3 min, cooled to −80° C.at 10° C./min, held at −80° C. for 3 min, and reheated from −80° C. at10° C./min (second heating). The crystallinity (wt %) is calculated fromthe second heating using a heat of fusion of 290 J/g for thepolyethylene crystal. Contributing effects of the crystallinity includedecrease volume fraction of the amorphous phase, restricted mobility ofthe amorphous chain segments by the crystalline domains, and higherstyrene content of the amorphous phase due to segregation of styreneinto the amorphous phase. Table I of this paper shows values of TotalStyrene (wt %), aPS (wt %), Styrene (wt %), Styrene (mol %), 10⁻³ Mw,Mw/Mn, and Talc (wt %) for Ethylene-styrene copolymers ES16–ES74 whileFIGS. 1–12 of this paper shows: (1) melting thermograms of ESI 1st and2nd heating for ES16, ES27, ES44, ES53, ES63, & ES74; (2) crystallinityfrom DSC as a function of comonomer content; (3) Logarithmic plot of theDSC heat of melting vs. Mole % ethylene for ESIs; (4) measured densityas a function of styrene content for semicrystalline and amorphous ESIs;(5)% crystallinity from density vs % crystallinity from DSC meltingenthalpy; (6) Dynamic mechanical relaxation behavior; (7) Glasstransition temperature as a function of wt % ethylene-styrene dyads forsemicrystalline and amorphous ESIs; (8) Arrhenius plots of the losstangent peak temperature for representative semicrystalline andamorphous ESIs; (9) Draw ratio vs engineering strain; (10) Engineeringstress-strain curves at 3 strain rates for ES27, ES63 and ES74; (11)Engineering stress-strain curves of ESIs; (12) Classification scheme ofESIs based on composition. (20) U.S. Pat. No. 5,872,201 describesinterpolymers: terpolymers of ethylene/styrene/propylene,ethylene/styrene/4-methyl-1-pentene, ethylene/styrene/hexend-1,ethylene/styrene/octene-1, and ethylene/styrene/norbornene with numberaverage molecular weight (Mn) of from 1,000 to 500,000. (21–24) U.S.Pat. Nos. 5,460,818; 5,244,996; EP 415815A; JP07,278,230 describessubstantially random, more appropriately presudo-random copolymers(interpolymers), methods of making and their uses. (25) Alizadeh, etal., find the styrene interpolymers impedes the crystallization ofshorter ethylene crystallizable sequences and that two distinctmorphological features (lamellae and fringe micellar or chain clusters)are observed in ethylene/styrene (3.4 mol %) as lamella crystalsorganized in stacks coexisting with interlamellar bridge-likestructures. (26) Guest, et al., describes ethylene-styrene copolymershaving less than about 45 wt % copolymer styrene being semicrystalline,as evidenced by a melting endotherm in DSC testing (Dupont DSC-901, 10°C./min) data from the second heating curve. Crystallization decreaseswith increasing styrene content. Based on steric hindrance, styrene unitis excluded from the crystalline region of the copolymers. Transitionfrom semi-crystalline to amorphous solid-state occurs at about 45 to 50wt % styrene. At low styrene contents (<40%), the copolymers exhibit arelatively well-defined melting process. FIGS. 1–5 of this paper shows(a) DSC data in the T range associated with the melting transition for arange of ESI differing primarily in copolymer styrene content, (b)variation in percent crystallinity (DSC) for ESI as a function ofcopolymer S content, (c) elastic modulus versus T for selected ESIdiffering in S content, (d) loss modulus versus T for selected ESIdiffering in S content, (e) Tensile stress/strain behavior of ESIdiffering in S content, respectively. (35) Hoening, et al, teachespreparation of interpolymers ESI #1 to #38 having number averagemolecular weight (Mn) greater than about 1000, from about 5,000 to about500,000, more specifically from about 10,000 to about 300,000. The abovepatents and publications are specifically incorporated herein byreference.

In general, the overall physical properties of amorphous gels are betterat higher gel rigidities. The amorphous gels, however, can failcatastrophically when cut or notched while under applied forces of highdynamic and static deformations, such as extreme compression, torsion,high tension, high elongation, and the like. Additionally, thedevelopment of cracks or crazes resulting from a large number ofdeformation cycles can induce catastrophic fatigue failure of amorphousgel s, such as tears and rips between the surfaces of the amorphous geland substrates or at the interfaces of interlocking material(s) and gel.Consequently, such amorphous gels are inadequate for the most demandingapplications involving endurance at high stress and strain levels overan extended period of time.

The various types of copolymers and block copolymers employed in formingthe crystal-gels of the invention are of the general configurations(Y-AY)_(n) copolymers, A-Z-A, and (A-Z)_(n) block copolymers, whereinthe subscript n is a number of two or greater. In the case of multiarmblock copolymers where n is 2, the block copolymer denoted by (A-Z)_(n)is A-Z-A. It is understood that the coupling agent is ignored for sakeof simplicity in the description of the (A-Z)_(n) block copolymers.

The segment (A) comprises a glassy amorphous polymer end block segmentwhich can be polystyrene, poly(alpha-methylstyrene),poly(o-methylstyrene), poly(m-methylstyrene), poly(p-methylstyrene) andthe like, preferably, polystyrene.

The segment (Y) of copolymers (Y-AY)_(n) comprises crystallizablepoly(ethylene) (simply denoted by “-E-” or (E)). In the case ofcopolymers (A-Y)_(n), (Y) when next to (A) may be substantiallynon-crystalline or amorphous ethylene segments. For example acrystalizable copolymer (Y-AY)_(n) may be represented by: . . .-E-E-E-E-E-E-E-E-E-SE-E-E-E-E-E-E-SE-E-E-E-E-E-E-SE- . . . . Where Y isa long run of polyethylene or a non-crystalline copolymer (AY-AY)_(n): .. . -E-SE-SE-E-SE-E-SE-E-SE-E-E-SE-SE-E-SE- . . . , where Y is anon-crystalline run of ethylene.

Other substantially random copolymers suitable for forming inventiongels of the invention include (Y-A-Y′) where Y is a crystalizable run ofethylene and Y′ can be propylene, 4-methyl-1-pentene, hexene-1,octene-1, and norborene. A can be styrene, vinyl toluene,alpha-methylstyrene, t-butylstyrene, chlorostyrene, including isomersand the like. Examples are: poly(ethylene-styrene) (ES),poly(ethylene-styrene-propylene) (ESP),poly(ethylene-styrene-4-methyl-1-pentene) (ES4M1P),poly(ethylene-styrene-hexend-1) (ESH1), poly(ethylene-styrene-octene-1)(ESO1), and poly(ethylene-styrene-norborene) (ESN),poly(ethylene-alpha-methylstyrene-propylene),poly(ethylene-alpha-methylstyrene-4-methyl-1-pentene),poly(ethylene-alpha-methylstyrene-hexend-1),poly(ethylene-alpha-methylstyrene-octene-1), andpoly(ethylene-alpha-methylstyrene-norborene) and the like.

The end block segment (A) comprises a glassy amorphous polymer end blocksegment which can be polystyrene, poly(alpha-methylstyrene),poly(o-methylstyrene), poly(m-methylstyrene), poly(p-methylstyrene) andthe like, preferably, polystyrene. The segment (Y) of random copolymersA-Y comprises crystalizable poly(ethylene) (simply denoted by “-E-” or(E)). In the case of random copolymers A-Y, (Y) may be substantiallynon-crystalline or amorphous ethylene segments. The midblocks (Z)comprises one or more midblocks of crystalizable poly(ethylene) (simplydenoted by “-E- or (E)”) with or without one or more amorphous midblocksof poly(butylene), poly(ethylene-butylene), poly(ethylene-propylene) orcombination thereof (the amorphous midblocks are denoted by “-B- or(B)”, “-EB- or (EB)”, and “-EP- or (EP)” respectively or simply denotedby “-W- or (W)” when referring to one or more of the amorphous midblocksas a group) The A and Z, and A and Y portions are incompatible and forma two or more-phase system consisting of sub-micron amorphous glassydomains (A) interconnected by (Z) or (Y) chains. The glassy domainsserve to crosslink and reinforce the structure. The number averagemolecular weight (Mn) of the random copolymers is preferably greaterthan 1,000, advantageously from about 5,000 to about 1,100,000, moreadvantageously from abut 8,000 to about 700,000. Examples are:

The method of making Y-A-Y and Y-A-Y′ random copolymers by metallocenesingle site catalysts are described in U.S. Pat. Nos. 5,871,201,5,470,993, 5,055,438, 5,057,475, 5,096,867, 5,064,802, 5,132,380,5,189,192, 5,321,106, 5,347,024, 5,350,723, 5,374,696, 5,399,635, and5,556,928, 5,244,996, application EP-A-0416815, EP-A-514828,EP-A-520732, WO 94/00500 all of which disclosure are incorporated hereinby reference.

The linear block copolymers are characterized as having a BrookfieldViscosity value at 5 weight percent solids solution in toluene at 30° C.of from less than about 40 cps to about 60 cps and higher,advantageously from about 40 cps to about 160 cps and higher, moreadvantageously from about 50 cps to about 180 cps and higher, still moreadvantageous from about 70 cps to about 210 cps and higher, and evenmore advantageously from about 90 cps to about 380 cps and higher.

The branched, star-shaped (radial), or multiarm block copolymers arecharacterized as having a Brookfield Viscosity value at 5 weight percentsolids solution in toluene at 30° C. of from about 80 cps to about 380cps and higher, advantageously from about 150 cps to about 260 cps andhigher, more advantageously from about 200 cps to about 580 cps andhigher, and still more advantageously from about 100 cps to about 800cps and higher.

The poly(ethylene/styrene) copolymers, type S series has more than 50 wt% styrene and is glassy at short times and rubbery at long times andexhibits ambient Tg, melt density of about higher than 0.952 to about0.929 and less, typical Mw=about less than 150,000 to 350,000 andhigher.

The type M series has more than 50 wt % styrene is amorphous rubber andexhibits very low modulus, high elasticity, low Tg of from greater than10° C. to less than −50, ° C., melt Index of from higher than 5 to lessthan about 0.1, melt density of higher than 0.93 to 9.0 and less,typical Mw=about less than 200,000 to 300,000 and higher.

The type E series contains up to 50 wt % styrene is semi-crystallinerubber and exhibits low Tg of from greater than 0° C. to about less than−70, low modulus semi-crystalline, good compression set, Melt Index offrom about higher than 2 to less than 0.03, melt density of about higherthan 0.90 to 0.805 and less, Mw=about less than 250,000 to 350,000 andhigher.

The E series random copolymers can be blended with the type M and type Sseries copolymers (having high glassy components) and one or more of thei, ii, iii, iv, v, vii and viii copolymers, plasticizers to formcrystalizable polymer invention gels of the invention.

This physical elastomeric network structure is reversible, and heatingthe polymer above the softening point of the glassy domains temporarilydisrupt the structure, which can be restored by lowering thetemperature. During mixing and heating in the presence of compatibleplasticizers, the glassy domains (A) unlock due to both heating andsolvation and the molecules are free to move when shear is applied. Thedisruption and ordering of the glassy domains can be viewed as aunlocking and locking of the elastomeric network structure. Atequilibrium, the domain structure or morphology as a function of the (A)and (Z) or (A) and (Y) phases (mesophases) can take the form of spheres,cylinders, lamellae, or bicontinous structures. The scale of separationof the phases are typically of the order of hundreds of angstroms,depending upon molecular weights (i.e. Radii of gyration) of theminority-component segments. The sub-micron glassy domains whichprovides the physical interlocking are too small to see with the humaneye, too small to see using the highest power optical microscope andonly adequately enough to see using the electron microscope. At suchsmall domain scales, when the gel is in the molten state while heatedand brought into contact to be formed with any substrate and allowed tocool, the glassy domains of the gel become interlocked with the surfaceof the substrate. At sufficiently high enough temperatures, with orwithout the aid of other glassy resins (such as polystyrene homopolymersand the like), the glassy domains of the copolymers forming the gelsfusses and interlocks with even a visibly smooth substrate surface suchas glass. The disruption of the sub-micron domains due to heating abovethe softening point forces the glassy domains to open up, unlocking thenetwork structure and flow. Upon cooling below the softing point, theglassy polymers reforms together into sub-micron domains, locking into anetwork structure once again, resisting flow. It is this unlocking andlocking of the network structure on the sub-micron scale with thesurfaces of various materials which allows the gel to form interlockings with other materials.

A useful analogy is to consider the melting and freezing of a watersaturated substrate, for example, foam, cloth, fabric, paper, fibers,plastic, concrete, and the like. When the water is frozen, the ice is toa great extent interlocked with the substrate and upon heating the wateris able to flow. Furthermore, the interlocking of the ice with thevarious substrates on close examination involves interconnecting ice in,around, and about the substrates thereby interlocking the ice with thesubstrates. A further analogy, but still useful is a plant or weed wellestablished in soil, the fine roots of the plant spreads out andinterconnects and forms a physical interlocking of the soil with theplant roots which in many instances is not possible to pull out theplant or weed from the ground without removing the surrounding soilalso.

Likewise, because the glassy domains are typically about 200 Angstromsin diameter, the physical interlocking involve domains small enough tofit into and lock with the smallest surface irregularities, as well as,flow into and flow through the smallest size openings of a poroussubstrate. Once the gel comes into contacts with the surfaceirregularities or penetrates the substrate and solidifies, it becomesdifficult or impossible to separate it from the substrate because of thephysical interlocking. When pulling the gel off a substrate, most oftenthe physically interlocked gel remains on the substrate. Even a surfacewhich may appear perfectly smooth to the eye, it is often not the case.Examination by microscopy, especially electron microscopy, will showserious irregularities. Such irregularities can be the source ofphysical interlocking with the gel.

Such interlocking with many different materials produce gel s havingmany uses including forming useful composites. The gel compositions isdenoted as “G” can be physically interlocked or formed in contact with aselected material denoted as “M” denoted for simplicity by theircombinations G_(n)M_(n), G_(n)M_(n)G_(n), M_(n)G_(n)M_(n),M_(n)G_(n)G_(n), G_(n)G_(n)M_(n), M_(n)M_(n)M_(n)G_(n),M_(n)M_(n)M_(n)G_(n)M_(n), M_(n)G_(n)G_(n)M_(n), G_(n)M_(n)G_(n)G_(n),G_(n)M_(n)M_(n)G_(n), G_(n)M_(n)M_(n)G_(n), G_(n)G_(n)M_(n)M_(n),G_(n)G_(n)M_(n)G_(n)M_(n), G_(n)M_(n)G_(n)G_(n), G_(n)G_(n)M_(n),G_(n)M_(n)G_(n)M_(n)M_(n), M_(n)G_(n)M_(n)G_(n)M_(n)G_(n),G_(n)G_(n)M_(n)M_(n)G_(n), G_(n)G_(n)M_(n)G_(n)M_(n)G_(n), and the likeor any of their permutations of one or more G_(n) with M_(n) and thelike, wherein when n is a subscript of M, n is the same or differentselected from the group consisting of foam, plastic, fabric, metal,concrete, wood, glass, ceramics, synthetic resin, synthetic fibers orrefractory materials and the like; wherein when n is a subscript of G, ndenotes the same or a different gel rigidity of from about 20 to about800 gram Bloom). The gel compositions and articles of the composites areformed from I, II, and III components described above.

Sandwiches of invention gel-material (i.e., inventiongel-material-invention gel or material-invention gel-material, etc.) areuseful as dental floss, shock absorbers, acoustical isolators, vibrationdampers, vibration isolators, and wrappers. For example the vibrationisolators can be use under research microscopes, office equipment,tables, and the like to remove background vibrations. The tearresistance nature of the invention gels are superior in performance toamorphous block copolymer gels which are much less resistance to crackpropagation caused by long term continue dynamic loadings.

The high tear resistant soft invention gels are advantageously suitablefor a safer impact deployable air bag cushions, other uses include:toys; games; novelty, or souvenir items; elastomeric lenses, lightconducing articles, optical fiber connectors; athletic and sportsequipment and articles; medical equipment and articles including dermause and for the examination of or use in normal or natural bodyorifices, health care articles; artist materials and models, specialeffects; articles designed for individual personal care, includingoccupational therapy, psychiatric, orthopedic, podiatric, prosthetic,orthodontic and dental care; apparel or other items for wear by and onindividuals including insulating gels of the cold weather wear such asboots, face mask, gloves, full body wear, and the like have as anessential, direct contact with the skin of the body capable ofsubstantially preventing, controlling or selectively facilitating theproduction of moisture from selected parts of the skin of the body suchas the forehead, neck, foot, underarm, etc; cushions, bedding, pillows,paddings and bandages for comfort or to prevent personal injury topersons or animals; housewares and luggage; articles useful intelecommunication, utility, industrial and food processing, and the likeas further described herein.

Cushion in the form of crumpets can be formed by utilizing the aerationmethod described in U.S. Pat. No. 4,240,905 (which is incorporatedherein by reference) instead of high solids, inert gas is introducedthrough a multi holed mold base at positive pressure depending on theworking viscosity of the molten invention gel and gel blends withoutrepeatedly shearing the rising injected gas streams thereby formingcushions having natural structures similar to crumpets upon cooling inthe mold. Also long metal netting needles of any desired diameter areprojected through multi holed mold base, top and side walls in variousdirections creating a multi directional hollowed network when molten gelis injected, poured, or transferred into the enclosed mold underpositive pressure and allowed to cool. The needles are easily removedone by one or altogether at once leaving the described multi channeledgel cushion. Likewise the inert gas injected into a gel body while inthe molten state can be sheared at desired time intervals so as toprovide hollowed cushions with any desired void shaped volumes. Acrumpet looks like a shaped volume with a smooth bottom and sidecontaining many small holes a few millimeter in diameter which holes areextended from near the bottom to the top of the crumpet.

Health care devices such as face masks for treatment of sleep disorderrequire non-tacky invention gels of the invention. The invention gel 3forming a gel overlap 7 portion on the face cup 1 at its edge 12conforming to the face and serve to provide comfort and maintain partialair or oxygen pressure when worn on the face during sleep. Other healthcase uses include pads in contact with the body use in wound healing andburn treatment, the gel can also be use as a needle protector sheath,tubing for medical fluid sets, as male and female connectors, sealingcaps, a pad use for compression at needle injection site to preventinjury to the blood vessel.

When utilized as a needle protector sheath, a invention gel compositionmade from SEEPS in combination with or without other polymers, andcopolymers is of advantage because of its higher rupture tear resistanceproperties. SEBS and SEPS in combination with low viscosity SEBS canalso be use to advantage, but with a noticeable decrease in ruptureresistance. The needle can be secured by forcing the sharp point intothe gel volume of a desired shaped gel body. In doing so, automaticallythe sharped needle is secured safely within the gel body preventing thesharp needle from accidently injuring the health worker or anyone elsein contact with the needle device. Moreover, the liquid be it medicationor body fluids are also securely and safely contained in the gel body.The gel automatically plug the tip of the sharp needle so as to preventany liquid from leaving the tip of the needle. Moreover the gel bodycontaining the needle can be in safe contact when accidently placed onor near a body while work is being performed. The holding power or forceholding the sharp needle can be adjusted by formulating the gel to anydesired rigidity. The greater the rigidity, the greater the holdingforce of the gel on the needle. Such needle can be inserted into a gelbody at any desired angle from less than 1° to less than 180° withoutloss of holding force on the needle. The gel needle protector sheath canbe any desired size. A large grip size is useful so as not to readilymisguide the needle into the gel body. A small size is useful so as notto be too bulky for storage. The requirement of the gel body as a needlesheath protector is that when drop from a height of 3 feet or 1 meter,the needle should not be able to penetrate through the gel body adjacentto the tip, thereby maintaining integrity of the seal and affordadequate protection to medical workers. The other requirement is thatthe gel body should have sufficient holding force gripping the needlewhile it rest within the gel body that it does not easily slip outaccidently. Such force can be selected to be greater than the weight ofthe needle and attached instrument the needle is physically attached. Arigidity in gram Bloom of greater than 100 gram is desirable forgripping the needle and hold it in place. Higher rigidity are ofadvantage, such as 100, 200, 300, 400, 500, 600, 800, 1000, 2000, andhigher.

Connectors, such as luer lock connectors, friction fit connectors, orother types of connectors for blood tubing especially useful fordialysis including use in connecting blood sets, hemodialysis tube sets,bubble trap inlet and outlet tubing, closures, caps and the like can becontaminated easily. A not so general information is that medical worksdo not take the time to decontaminate or safe guard connectors. Theconnectors are plug in and unplugged when needed and almost no one seeto the cleanliness of the connectors before plug the connectorstogether, there is just no time for it. The need to plug and unplugconnectors in the health service environment is that the connectors comein two types: male and female use to make every connection and the maleand female parts come separately because at the time of manufacture theyare made separately. The invention gel of high rigidity made from gelcompositions of 250 to 400 parts by weight of block copolymers areuseful for making tubing and tubing connectors. Surprisingly, if a malemold is use to made the male connector part, the male connector part canbe allowed to cool in the mold and the same mold holding the maleconnector part can than be injected with additional gel of suitablerigidity to form the opposite female part. When the mold containing themale and female connector parts are cooled sufficient, both male andfemale connectors are demoted at the same time and packaged withoutcontamination. The connectors can be molded with the same gel materialtubing or if molded separately, the connectors need not be taken apartuntil needed. The novelty is that when the invention gels aresufficiently cooled to above room temperature, a second and followed bya third and the like molten gel can be in contact with the cooled geland when both have cooled sufficiently the two parts will come apart.They do not bond in any way. Therefore a gel article negative canreceive molten gel utilizing the negative get to form a positive. Thisreduces the cost of making two molds, a positive and a negative. Onlyone is necessary to make both parts.

Tacky gels because of its tactile feel are undesirable for suchapplications while other application require gel adhesion to the skinand selected substrates. Gels are inherently sticky or tacky to thetouch, especially soft thermoplastic elastomer oil gels which canexhibit extreme tackiness when compounded with high viscosity oils. Thetackiness can be reduced, masked or removed by powdering the gel'soutside surface or by incorporating additives which will eventuallymigrate to the gel's outer surface. Such additives being effective onlyat the gel's surface. The migration of additives from within the bulkgel to the gel's surface is generally due to gradients of pressure ortemperature, weak, moderate, or strong molecular dipo/dipo ordipo/non-dipo interactions within the gel. The additives, however, cancause the gels to be translucent or opaque throughout their volume asfound in my U.S. Pat. No. 5,760,117 which describes surface activatednon-tacky gels. Once the additives are transported from within the gelto the surface forming an “additive layer”. Although the additive layercan reduced tackiness or no tack at the gel's surface, the additivelayer can themselves impart their own tactical character. For example,stearic acid exhibits a low melting point and tends to be somewhatgreasy at ambient or above ambient temperatures. Once the gel is damagedor cut, the tackiness of the freshly cut area is exposed.

Stearic acid and other additives such as certain organic crystals willmelt upon heating and reform into crystals within the gel and may bloomto the gel surface as described in my U.S. Pat. No. 6,420,475. Selectedsubstances blended into a gel will eventually find its way from theinterior of the bulk gel to its surface by means of migration due togradient transport (bloom to the surface with time depending on thenature of the added substances).

As use herein, the tack level in terms of “Gram Tack” is determined bythe gram weight displacement force to lift a polystyrene referencesurface by the tip of a 16 mm diameter hemi-spherical gel probe incontact with said reference surface as measured on a scale at 23° C.(about STP conditions).

As used herein, the term “gel rigidity” in gram Bloom is determined bythe gram weight required to depress a gel a distance of 4 mm with apiston having a cross-sectional area of 1 square centimeter at 23° C.

The gelatinous elastomer compositions of the present invention can bemade firm or soft, tacky, adherent or non-tacky to the touch. The“non-tacky to the touch” gelatinous elastomer compositions of theinvention is not based on additives which bloom to the surface to reducetack. For simplicity, the gelatinous elastomer compositions of theinvention (which are highly tear resistant and rupture resistant and canbe made tacky, adherent, non-tacky to the touch and opticallytransparent or clear) will be referred to herein as “invention gel(s)”which includes “tear resistant gels”, “rupture resistant gels”,“non-tacky gels”, “no tack gels”, “optical gels”, “tacky gels”,“adherent gels”, and the like when referring to certain propertyattributes of the various gels or more simply refer to as “the gel(s)”or “said gel(s)”. Gels of the invention are described herein below forevery use.

As described herein, the conventional term “major” means greater than 50parts by weight and higher (e.g. 5.01, 50.2, 50.3, 50.4, 50.5, . . . 51,52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69,. . . 580 and higher based on 100 part by weight of (1) copolymers) andthe term “minor” means 49.99 parts by weight and lower (e.g. 49, 48, 47,46, 45, 44, 43, 42, 41, 40, 39, 38, 37, 36, 35, 34, 33, 32, 21, . . .10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7 . . . 0.09 and the like)based on 100 parts by weight of the base (I) block copolymer(s).

It should be understood that although the conventional term “parts byweight” is used, the term “parts by weight” is ordinarily used in rubbertire and rubber goods and other formulations. This terms or method offormulation is especially useful and easy to keep track of changes madein formulation work as changes are often needed to arrive at an optimumformulation to improve one property or another. Each of the componentswhich go into a formulation are weight out, except for the “rubber” orbase “polymer” which is kept at a constant “100 parts by weight”. Asimple notation is “hpr” or “hundred parts of rubber” or “pphr” whichspells out to read “parts per hundred of rubber”.

Any units of weight measure can be use, depending on the available scaleused (grams, pounds, oz, etc.). Parts by weight is useful, because notevery one on uses the same units of measure. One can convert from “100parts by weight of rubber” to weight %. For example, “parts by weight of(b)” and “parts by weight of (c)” are based with respect to 100 parts byweight of component “(a)”:

A formulation based on parts by weight can be calculated as follows: Addto 100 parts by weight of elastomer “A”, 300 parts by weight oil “B”, 49parts by weight resin “C”. This formulation has a total weight of “449”which can be in grams, pounds, tons, whatever unit of weight measurementused. In order to convert this formulation into %, we simply divide eachof the components by 449″ resulting: %A=(100/449)×100=(0.2227271)×100=22.27271%=elastomer, %B=(300/449)×100=(0.6681514)×100=66.81514%=oil, %C=(49/449)×100=(0.1091314)×100=10.91314%=resin, and a Total %=99.99999%or 100%

If we performed the measurements in grams, than 100 grams of formulation“ABC” would simply contain 22.27271 grams elastomer, 66.81514 grams ofoil, and 10.91314 grams of resin. Consistent with this hundred year oldmethodology are the terms minor and major with respect to “100 parts byweight of rubber”. An amount less than about 50 parts by weight withrespect to “100 parts by weight of rubber” would be considered “minoramount.” An amount greater than 50 parts by weight with respect to “100parts by weight of rubber” would be considered “major amount.”

Gels are inherently sticky or tacky to the touch, especially softthermoplastic elastomer oil gels which can exhibit extreme tackinesswhen compounded with high viscosity oils. The tackiness can be reduced,masked or removed by powdering the gel's outside surface or byincorporating additives which will eventually migrate to the gel's outersurface. Such additives being effective only at the gel's surface. Themigration of additives from within the bulk gel to the gel's surface isgenerally due to gradients of pressure or temperature, weak, moderate,or strong molecular dipo/dipo or dipo/non-dipo interactions within thegel. The additives, however, can cause the gels to be translucent oropaque throughout their volume as found in my U.S. Pat. No. 5,760,117which describes surface activated non-tacky gels. Once the additives aretransported from within the gel to the surface forming an “additivelayer”. Although the additive layer can reduced tackiness or no tack atthe gel's surface, the additive layer can themselves impart their owntactical character. For example, stearic acid exhibits a low meltingpoint and tends to be somewhat greasy at ambient or above ambienttemperatures. Once the gel is damaged or cut, the tackiness of thefreshly cut area is exposed.

Not only can the invention gels be made tacky and adherent to any degreedesired or non-tacky to the touch, the gels are naturally transparent,and optically clear suitable for optical use. The gels are strong,elastic, highly tear resistant, and rupture resistant. The inventiongels can be formed into any shape for the intended use such as solidshapes for use as articles of manufacture, thin and thick sheets,strands, strings, ropes, fibers, fine silk like filaments can be appliedin its molten state onto various substrates as s.

The invention gels of the invention can be formed into gel strands, gelbands, gel tapes, gel sheets, and other articles of manufacture incombination with or without other substrates or materials such asnatural or synthetic fibers, multifibers, fabrics, films and the like.Moreover, because of their improved tear resistance and resistance tofatigue, the invention gels exhibit versatility as balloons for medicaluses, such as balloon for valvuloplasty of the mitral valve,gastrointestinal balloon dilator, esophageal balloon dilator, dilatingballoon catheter use in coronary angiogram and the like. Since theinvention gels are more tear resistant, they are especially useful formaking condoms, toy balloons, and surgical and examination gloves. Astoy balloons, the invention gels are safer because it will not ruptureor explode when punctured as would latex balloons which often timescause injures or death to children by choking from pieces of latexrubber. The invention gels are advantageously useful for making gloves,thin gloves for surgery and examination and thicker gloves for vibrationdamping which prevents damage to blood capillaries in the fingers andhand caused by handling strong shock and vibrating equipment. Variousother gel articles can be made from the advantageously tear resistantgels and gel s of the inventions include gel suction sockets, suspensionbelts.

The invention gels are also useful for forming orthotics and prostheticarticles such as for lower extremity prosthesis described below.

Advantageously, the invention gels of the invention are non-tackyrequires no additive. Its non-tackiness are an inherent property of thecrystallinity, glassy A components, and selected low viscosityplasticizers forming the invention gels of the invention. Such inventiongels, however, must met the following criteria:

(a) the invention gels are made from A-Z-A, (A-Z)_(n), (A-Y)_(n),(Y-AY)_(n) and (Y-AY′)_(n) copolymers: crystalizable block copolymersand crystalizable poly(ethylene-styrene) substantially random copolymersof the type S, M, and E series (for example SEEPS, S-E-EB-S,S-EB45-EP-S, S-E-EB25-S, S-E-EP-E-S, S-EP-E-S, S-EP-E-EP-S, E-S-E,(E-S)_(n), (E-S-E)_(n), (ESP), (ES4M1P), (ESH1), (ESO1), (ESN) and(S-E-EP)_(n), crystalizable S-EB-S with elastomeric crystalizableblock:glassy block ratios of 89:11, 88:12, 87:13, 86:14, 85:15, 84:16,83:17, 82:18, 81:19, 80:20, 79:21, 78:22, 77:23, 76:24, 75:25, 74:26,73:27, 72:28, 71:29, and 70:30) and the like;

(b) the invention gels are made from copolymers having crystalizablepoly(ethylene) segments exhibit melting exdotherm values and in betweenof about 10° C., 20° C., 25° C., 26° C., 27° C., 28° C., 29° C., 30° C.,31° C., 32° C., 33° C., 34° C., 35° C., 36° C., 37° C., 38° C., 39° C.,40° C., 41° C., 42° C., 43° C., 44° C., 44° C., 45° C., 46° C., 47° C.,48° C., 49° C., 50° C., 51° C., 52° C., 53° C., 54° C., 55° C., 56° C.,57° C., 58° C., 59° C., 60° C., 61° C., 62° C., 63° C., 64° C., 65° C.,66° C., 67° C., 68° C., 69° C., 70° C., 71° C., 72° C., 73° C., 74° C.,75° C., 76° C., 78° C., 79° C., 80° C., and higher; and

(c) the invention gels are made from copolymers having glassy A to Y orglassy A to Z ratios of at least 37:63, higher ratios are also ofadvantage, such as: 38:62, 39:61, 40:60, 41:59, 42:58, 43:57, 44:65,45:55, 46:54, 47:53, 48:52, 49:51, 50:50, 51:49, 52:48, 53:47, 54:46,55:45, 56:44, 57:43, 58:42, 59:41, 60:40, 61:39, 62:38, 63:37, 64:36,65:35, 66:34; or by the addition of

(d) sufficient amounts of glassy homopolymers or glass associated phaseresins so that condition (c) is met.

It is believed that the combination of sufficient amounts ofcrystallinity and sufficient amounts glassy A components of thecopolymers in combination with low viscosity plasticizers impartsnon-tackiness to the invention gels of the invention. It is thereforecontemplated that the same effect can be achieved by blending highlycrystalizable and highly glassy copolymers (Dow S, M, & E Series E-S-E),with less crystalizable and less glassy copolymers such as amorphousSEPS, SEBS, and amorphous S-EB-EP-S and other amorphous copolymersprovided the amorphous copolymers are in minor amounts and there issubstantial crystallinity and sufficient over all glassy A components tomeet conditions (c).

The glassy homopolymers of (d) are advantageously selected from one ormore homopolymers of: polystyrene, poly(alpha-methylstyrene),poly(o-methylstyrene), poly(m-methylstyrene), poly(p-methylstyrene), andpoly(dimethylphenylene oxide). The average molecular weight of theglassy homopolymers advantageously can range from and in between about2,500 to about 90,000, typical about 3,000; 4,000; 5,000; 6,000; 7,000;8,000; 9,000; 10,000; 11,000; 12,000; 13,000; 14,000; 15,000; 16,000;17,000; 18,000; 19,000; 20,000; 30,000; 40,000; 50,000; 60,000; 70,000;80,000; 90,000 and the like. Example of various molecular weights ofcommercially available polystyrene: Aldrich Nos.: 32,771-9 (2,500M_(w)), 32,772-7 (4,000 Mw), 37,951-4 (13,00 Mw), 32-774-3 (20,000 Mw),32,775-1 (35,000 Mw), 33,034-5 (50,000 Mw), 32,777-8 (90,000 Mw);poly(alpha-methylstyrene) #41,794-7 (1,300 Mw), 19,184-1 (4,000 Mw);poly(4-methylstyrene) #18,227-3 (72,000 Mw), Endex 155, 160, Kristalex120, 140 from Hercules Chemical, GE; Blendex HPP820, HPP822, HPP823, andthe like. Various glassy phase associating resins having softeningpoints above about 120° C. can also serve to increase the glassy phaseof the invention gels of the invention and met the non-tackinesscriteria, these include: Hydrogenated aromatic resins (Regalrez 1126,1128, 1139, 3102, 5095, and 6108), hydrogenated mixed aromatic resins(Regalite R125), and other aromatic resin (Picco 5130, 5140, 9140, CumarLX509, Cumar 130, Lx-1035) and the like.

On the other hand, the molten gelatinous elastomer composition willadhere sufficiently to certain plastics (e.g. acrylic, ethylenecopolymers, nylon, polybutylene, polycarbonate, polystyrene, polyester,polyethylene, polypropylene, styrene copolymers, and the like) providedthe temperature of the molten gelatinous elastomer composition issufficient high to fuse or nearly fuse with the plastic. In order toobtain sufficient adhesion to glass, ceramics, or certain metals,sufficient temperature is also required (e.g. above 250° F.). Commercialresins which can aid in adhesion to materials (plastics, glass, andmetals) may be added in minor amounts to the gelatinous elastomercomposition, these resins include: Super Sta-tac, Nevtac, Piccotac,Escorez, Wingtack, Hercotac, Betaprene, Zonarez, Nirez, Piccolyte,Sylvatac, Foral, Pentalyn, Arkon P, Regalrez, Cumar LX, Picco 6000,Nevchem, Piccotex, Kristalex, Piccolastic, LX-1035, and the like.

The commercial resins which can aid in adhesion to materials (plastics,glass, and metals) may be added in minor amounts to the gelatinouselastomer composition, these resins include: polymerized mixed olefins(Super Sta-tac, Betaprene Nevtac, Escorez, Hercotac, Wingtack,Piccotac), polyterpene (Zonarez, Nirez, Piccolyte, Sylvatac), glycerolester of rosin (Foral), pentaerythritol ester of rosin (Pentalyn),saturated alicyclic hydrocarbon (Arkon P), coumarone indene (Cumar LX),hydrocarbon (Picco 6000, Regalrez), mixed olefin (Wingtack), alkylatedaromatic hydrocarbon (Nevchem), Polyalphamethylstyrene/vinyl toluenecopolymer (Piccotex), polystyrene (Kristalex, Piccolastic), specialresin (LX-1035), and the like. More earlier, I had also disclosed theuse of liquid tackifiers in high viscosity SEBS gels.

The incorporation of such adhesion resins is to provide strong anddimensional stable adherent invention gels, gel s, and gel articles.Typically such adherent invention gels can be characterized as adhesivegels, soft adhesives or adhesive sealants. Strong and tear resistantadherent invention gels may be formed with various combinations ofsubstrates or adhere (attach, cling, fasten, hold, stick) to substratesto form adherent invention gel/substrate articles and s.

Various substrate and adherent invention gel combinations which can beutilized to form adherent invention gel articles include: G_(n)M_(n),G_(n)G_(n), G_(n)M_(n)G_(n), M_(n)G_(n)M_(n), M_(n)G_(n)G_(n),G_(n)G_(n)M_(n), G_(n)G_(n)M_(n), G_(n)M_(n)M_(n)G_(n),M_(n)G_(n)G_(n)M_(n), M_(n)M_(n)G_(n)G_(n), M_(n)M_(n)M_(n)G_(n)G_(n),G_(n)M_(n)G_(n)G_(n), G_(n)M_(n)G_(n)M_(n)M_(n),M_(n)G_(n)M_(n)G_(n)M_(n)G_(n)M_(n), or any permutations of saidcombination, where G=gel and M=material. The subscript 1, 2, 3, 4, etc.,are different and is represented by n which is a positive number, when nis a subscript of M, n may be the same or different material and when nis a subscript of G, n can be the same or different rigidity adherentinvention gel or the same or different adherent invention gel materialcomposition. The material (M) suitable for forming articles with thegelatinous elastomer compositions can include foam, plastic, fabric,metal, concrete, wood, wire screen, refractory material, glass,synthetic resin, synthetic fibers, and the like. Sandwiches of adherentinvention gel/material (i.e. adherent invention gel-material-adherentinvention gel or material-adherent invention gel-material, etc.) areideal for use as shock absorbers, acoustical isolators, vibrationdampers, vibration isolators, and wrappers. For example the vibrationisolators can be use under research microscopes, office equipment,tables, and the like to remove background vibrations.

Various useful adhesion resins of one or more types can be incorporatedin minor amounts into the adherent invention gel. These include:polymerized mixed olefins, polyterpene, glycerol ester of rosin,pentaerythritol ester of rosin, saturated alicyclic hydrocarbon,coumarone indene, hydrocarbon, mixed olefin, alkylated aromatichydrocarbon, Polyalphamethylstyrene/vinyl toluene copolymer,polystyrene, special resin, and the like.

The adherent invention gel compositions of the invention can be castedunto various substrates, such as foam, plastic, fabric, metal, concrete,wood, wire screen, refractory material, glass, synthetic resin,synthetic fibers, and the like, or the adherent invention gels formedand then can be adhere (attach, cling, fasten, hold, stick) to thedesired substrates to form various G_(n)M_(n), G_(n)G_(n),G_(n)M_(n)G_(n), M_(n)G_(n)M_(n), M_(n)G_(n)G_(n), G_(n)G_(n)M_(n),G_(n)G_(n)M_(n), G_(n)M_(n)M_(n)G_(n), M_(n)G_(n)G_(n)M_(n),M_(n)M_(n)G_(n)G_(n), M_(n)M_(n)M_(n)G_(n)G_(n), G_(n)M_(n)G_(n)G_(n),G_(n)M_(n)G_(n)M_(n)M_(n), M_(n)G_(n)M_(n)G_(n)M_(n)G_(n)M_(n), or anypermutations of said combination s for uses requiring temporary peel andre-use as well as permanent long-life use as needed. Adhesion tosubstrates is most desirable when it is necessary to apply the adherentinvention gels to substrates in the absence of heat or on to a lowtemperature melting point substrate for later peel off after use, suchas for sound damping of a adherent invention gel applied to a firstsurface and later removed for use on a second surface. The low meltingsubstrate materials which can not be exposed to the high heat of themolten adherent invention gels, such as low melting metals, low meltingplastics (polyethylene, PVC, PVE, PVA, and the like) can only be formedby applying the adherent invention gels to the temperature sensitivesubstrates. Other low melting plastics include: polyolefins such aspolyethylene, polyethylene copolymers, ethylene alpha-olefin resin,ultra low density ethylene-octene-1 copolymers, copolymers of ethyleneand hexene, polypropylene, and etc. Other cold applied adherentinvention gels to teflon type polymers: TFE, PTFE, PEA, FEP, etc.,polysiloxane as substrates are achieved using the adherent inventiongels of the invention.

Likewise, adherent invention gel substrate s can be both formed bycasting hot onto a substrate and then after cooling adhering theopposite side of the adherent invention gel to a substrate having a lowmelting point. The adherent invention gel is most essential when it isnot possible to introduce heat in an heat sensitive or explosiveenvironment or in outer space. The use of solid or liquid resinspromotes adherent invention gel adhesion to various substrates bothwhile the adherent invention gel is applied hot or at room temperatureor below or even under water. The adherent invention gels can be appliedwithout heating to paper, foam, plastic, fabric, metal, concrete, wood,wire screen, refractory material, glass, synthetic resin, syntheticfibers, and the like.

The adhesion properties of the gels are determined by measuringcomparable rolling ball tack distance “D” in cm using a standarddiameter “d” in mm stainless steel ball rolling off an inclined ofheight “H” in cm and determining the average force required to perform180° peel of a heat formed G₁M₁ one inch width sample applied at roomtemperature to a substrate M₂ to form the M₁G₁M₂ The peel at a selectedstandard rate cross-head separation speed of 25 cm/minute at roomtemperature is initiated at the G₁M₂ interface of the M₁G₁M₂, where thesubstrate M₂ can be any of the substrates mentioned and M₁ preferably aflexible fabric.

Advantageously, glassy phase associating homopolymers such aspolystyrene and aromatic resins having low molecular weights of fromabout 2,500 to about 90,000 can be blended with the triblock copolymersof the invention in large amounts with or without the addition ofplasticizer to provide a copolymer-resin alloy of high impact strengths.More advantageously, when blended with multiblock copolymers andsubstantially random copolymers the impact strengths can be even higher.The impact strength of blends of from about 150 to about 1,500 parts byweight glass phase associating polymer and resins to 100 parts by weightof one or more multiblock copolymers can provide impact strengthapproaching those of soft metals. At the higher loadings, the impactstrength approaches that of polycarbonates of about 12 ft-lb/in notchand higher.

The improvements of the invention gels of the invention is exceptional,the invention gels are invention to the touch and can be quantifiedusing a simple test by taking a freshly cut Invention gel probe of aselected gel rigidity made from the invention gels of the invention. Theinvention gel probe is a substantially uniform cylindrical shape oflength “L” of about 3.0 cm formed components (1)–(3) of the inventiongels of the invention in a 16×150 mm test tube. The invention gel probeso formed has a 16 mm diameter hemi-spherical tip which (not unlike theshape of a human finger tip) is brought into perpendicular contact aboutsubstantially the center of the top cover of a new, un-touchedpolystyrene reference surface (for example the top cover surface of asterile polystyrene petri dish) having a diameter of 100 mm and a weightof 7.6 gram resting on its thin circular edge (which minimizes thevacuum or partial pressure effects of one flat surface in contact withanother flat surface) on the flat surface of a scale which scale istared to zero. The probe's hemi-spherical tip is place in contact withthe center of the top of the petri dish cover surface and allowed toremain in contact by the weight of the gel probe while held in theupright position and then lifted up. Observation is made regarding theprobe's tackiness with respect to the clean reference polystyrenesurface. For purpose of the foregoing reference tack test, tackinesslevel 0 means the polystyrene dish cover is not lifted from the scale bythe probe and the scale shows substantially an equal positive weight andnegative weight swings before settling again back to zero with the swingindicated in (negative) grams being less than 1.0 gram. A tackinesslevel of one 1, means a negative swing of greater than 1.0 gram but lessthan 2.0 gram, tackiness level 2, means a negative swing of greater than2 gram but less than 3 gram, tackiness level 3, means a negative swingof greater than 3 gram but less than 4 gram, before settling back to thezero tared position or reading. Likewise, when the negative weight swingof the scale is greater than the weight of the dish (i.e., for theexample referred above, greater than 7.6 gram), then the scale shouldcorrectly read −7.6 gram which indicates the dish has completely beenlifted off the surface of the scale. Such an event would demonstrate thetackiness of a gel probe having sufficient tack on the probe surface.The invention gels of the invention fails to lift off the polystyrenereference from the surface of the scale when subject to the foregoingreference tack test. Advantageously, the invention gels of the inventioncan register a tackiness level of less than 5, more advantageously, lessthan 3, still more advantageously, less than 2, and still moreadvantageously less than 1. The non-tackiness of the invention gels ofthe invention can advantageously range from less than 6 to less than 0.5grams, typical tack levels are less than or in between about 0.2, 0.3,0.4, 0.5, 0.6, 0.7. 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7,1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.5, 2.8, 3.0, 3.5, 4.0, 4.5, 5.0 gramsand the like. Whereas probes of gels made from amorphous gels such asSEPS, SEBS, S-EP-EB-S, and the like with copolymer styrene to rubberratio of less than 37:63 and plasticizer of higher than 30 cSt 40° C.are found to lift the polystyrene reference from the surface of thescale. For purposes of indicating tack, the method above can provide geltack level readings of 1, 2, 3, 4, 5, 6, and 7 grams. More accurate andsensitive readings can be made using electronic scales of tack levels ofless than 1 gram. By this simple method tack levels (of a gel probe on apolystyrene reference surface) can be measure in terms of gram weightdisplacement of a scale initially tared to zero. For purpose of thepresent invention the method of using a polystyrene reference surfacehaving a weight of 7.6 grams in contact and being lifted by thetackiness of a cylindrical gel probe having a 16 mm diameterhemi-spherical tip is used to determine the tackiness of the inventiongels of the invention. The level of tack being measured in gram Tack at23° C.

The improvements of other properties of the invention gels overamorphous gels are many, these include: improved damage tolerance,improved crack propagation resistance, improved tear resistance,improved resistance to fatigue, etc. Such invention gels areadvantageous for end-use involving repeated applications of stress andstrain resulting from large number of cycles of deformations, includingcompression, compression-extension (elongation), torsion,torsion-compression, torsion-elongation, tension, tension-compression,tension-torsion, etc. The invention gels also exhibit improved damagetolerance, crack propagation resistance and especially improvedresistance to high stress rupture which combination of properties makesthe gels advantageously and surprisingly exceptionally more suitablethan amorphous gels made from non-crystalline poly(ethylene) componentcopolymers at corresponding gel rigidities.

Block copolymers with polyethylene midblocks alone do not form suitableInvention gels for purpose of the invention. Crystalizable midblockregions needs to be balanced with amorphous midblock regions in order toobtain soft, flexible and elastic gels with the desired crystalizableproperties that are not found in totally amorphous gels.

The various representative glassy domain/amorphous structures ofS-E-EB-S, S-E-EB₂₅-S, S-E-EP-E-S, S-EP-E-S and S-EP-E-EP-S. Although thestructure are spheroid representation, cylinders and plates are alsowithin the scope of the present invention. Cylinder and plate structureare obtained with increasing glassy A end blocks. From about 15–30% byweight of A blocks, the block copolymer structure is spheroid. Fromabout 33 about 40% by weight of A blocks, the block copolymer structurebecomes cylindrical; and above about 45% A blocks, the structure becomesless cylindrical and more plate like.

In order to obtain elastic invention gels of the invention, it isnecessary that the selective synthesis of butadiene produce sufficientamounts of 1,4 poly(butadiene) that on hydrogenation can exhibit“crystallinity” in the midblocks. In order for the block copolymersforming the invention gels of the invention to exhibit crystallinity,the crystalizable midblock segments must contain long ruts of —CH₂—groups. There should be approximately 16 units of —(CH₂)— in sequencefor crystallinity. Only the (—CH₂—)₄ units can crystallize, and thenonly if there are 4 units of (—CH₂—)₄ in sequence; alternatively, thepolyethylene units are denoted by [—(CH₂—CH₂—CH₂—CH₂)—]₄, [(—CH₂—)₄]₄ or(—CH₂—)16. The amount of (—CH₂—)16 units forming the (E) midblocks ofthe block copolymers comprising the invention gels of the inventionshould be about 20% which amount is capable of exhibiting a meltingendotherm in differential scanning calorimeter (DCS) curves.

Advantageously, the elastomer midblock segment should have acrystallinity of about 20% of (—CH₂—)16 units of the total mole %forming the midblocks of the block copolymer, more advantageously about25%, still more advantageously about 30%, especially advantageouslyabout 40% and especially more advantageously about 50% and higher.Broadly, the crystallinity of the midblocks should range from about 20%to about 60%, less broadly from about 18% to about 65%, and still lessbroadly from 22% to about 70%.

The melting exdotherm in DSC curves of the crystalizable blockcopolymers comprising about 20% crystallinity of the polyethyleneportion of the midblock are much higher than conventional amorphousblock copolymers. The poly(ethylene) crystalizable segments or midblocksof copolymers forming the invention gels of the invention arecharacterized by sufficient crystallinity as to exhibit a exdotherm asdetermined by DSC curve. The maximum in the endotherm curves of thecrystalizable copolymers curs at about 40° C., but can range fromgreater than about 25° C. to about 60° C. and higher. The crystalizablecopolymers forming the invention gels of the invention can exhibitmelting endotherms (as shown by DSC) of about 25° C. to about 75° C. andhigher. More specific melting exdotherm values of the crystalizableblock copolymers include: about 8° C., 10° C., 20° C., 28° C., 29° C.,30° C., 31° C., 32° C., 33° C., 34° C., 35° C., 36° C., 37° C., 38° C.,39° C., 40° C., 41° C., 42° C., 43° C., 44° C., 45° C., 46° C., 47° C.,48° C., 49° C., 50° C., 51° C., 52° C., 53° C., 54° C., 55° C., 56° C.,57° C., 58° C., 59° C., 60° C., 61° C., 62° C., 63° C., 64° C., 65° C.,66° C., 67° C., 68° C., 69° C., 70° C., 71° C., 72° C., 73° C., 74° C.,75° C., 76° C., 77° C., 78° C., 79° C., 80° C., 90° C., 100° C., 110°C., 120° C., and higher, whereas, the melting endotherm (DSC) forconventional amorphous midblock segment block copolymers are about 10°C. and lower.

The melting endotherm is seen on heating and a sharp crystallizationexotherm is seen on cooling. Such midblock crystallization endothermicand exothermic characteristics are missing from DSC curves of amorphousgels. The crystallization exotherm and fusion endotherm of thecrystalizable block copolymer gels of the invention are determined byASTM D 3417 method.

Generally, the method of obtaining long runs of crystalizable —(CH₂)— isby sequential block copolymer synthesis followed by hydrogenation. Theattainment of invention gels of the instant invention is solely due tothe selective polymerization of the butadiene monomer (forming themidblocks) resulting in one or more predetermined amount of 1,4poly(butadiene) blocks followed by sequential polymerization ofadditional midblocks and hydrogenation to produce one or morecrystalizable midblocks of the final block copolymers.

Hydrogenated polyisoprene midblocks remain amorphous, while hydrogenatedpolybutadiene midblocks can be either amorphous or crystallizabledepending upon their structure. Polybutadiene can contain either a 1,2configuration, which hydrogenates to give the equivalent of a 1-butenerepeat unit, or a 1,4-configuration, which hydrogenates to give theequivalent of an ethylene repeat unit. Polybutadiene midblocks havingapproximately 40 weight percent 1,2-butadiene content, based on theweight of the polybutadiene midblock, provides substantially amorphousblocks with low glass transition temperatures upon hydrogenation.Polybutadiene midblocks having less than approximately 40 weight percent1,2-butadiene content, based on the weight of the polybutadienemidblock, provide crystalizable midblocks upon hydrogenation. Theconjugated diene polymer midblock may also be a copolymer of more thanone conjugated diene, such as a copolymer of butadiene and isoprene.Where the midblock of the block copolymer contains more than oneconjugated diene polymer block, such as a polybutadiene block and apolyisoprene block, hence hydrogenated midblock can be EB/EP or E/EPdepending on the presence and amount of polybutadiene 1,2 and 1,4microstructure.

The crystalizable block copolymers are made by sequential blockcopolymer synthesis, the percentage of crystallinity or (—CH₂—)₁₆ unitsshould be about (0.67)₄ or about 20% and actual crystallinity of about12%. For example, a selectively synthesized S-EBn-S copolymer having aratio of 33:67 of 1,2 and 1,4 poly(butadiene) on hydrogenation willresult in a midblock with a crystallinity of (0.67)₄ or 20%. For sake ofsimplicity, when n is a subscript of -EB-, n denotes the percentage of(—CH₂—)₄ units, eg, n=33 or 20% crystallinity which is the percentage of(0.67)₄ or “(—CH₂—)₁₆” units. Thus, when n=28 or 72% of (—CH₂—)₄ units,the % crystallinity is (0.72)₄ or 26.87% crystallinity attributed to(—CH₂—)₁₆ units, denoted by -EB₂₈-. As a matter of convention, and forpurposes of this specification involving hydrogenated polybutadiene: thenotation -E- denotes about 85% of (—CH₂—)₄ units. The notation -B-denotes about 70% of [—CH₂—CH(C₂H₅)—] units. The notation -EB- denotesbetween about 15 and 70% [—CH₂—CH(C₂H₅)—] units. The notation -EBn-denotes n % [—CH₂—CH(C₂H₅)—] units. For hydrogenated polyisoprene: Thenotation -EP- denotes about 90% [—CH₂—CH(CH₃)—CH₂—CH₂—] units.

Generally, one or more (E) midblocks can be incorporated at variouspositions along the midblocks of the block copolymers. Using thesequential process for block copolymer synthesis, The (E) midblocks canbe positioned as follows:

a) A-E-W-A b) A-E-W-E-A c) A-W-E-W-A d) A-E-W-E-W-E-W-E-A e)A-W-E-W-A-E-A-E-W-E-A f) and etc.

The lower flexibility of block copolymer invention gels due to (E)midblocks can be balanced by the addition of sequentially (W) midblocks.For example, the sequentially synthesized block copolymer S-E-EB-S canmaintain a high degree of flexibility due to the presence of amorphous-EB- block. The sequential block copolymer S-E-EB-B-S can maintain ahigh degree of flexibility due to the presence of amorphous -EB- and -B-midblocks. The sequential block copolymer S-E-EP-E-S can maintain a highdegree of flexibility due to the presence of -EP- midblock. Thesequential block copolymer S-E-B-S can maintain a high degree offlexibility due to the presence of the -B- midblock. For S-E-S, wherethe midblock is crystalizable and flexibility low, physical blendingwith amorphous block copolymers such as S-EB-S, S-B-S, S-EP-S,S-EB-EP-S, (S-EP)_(n) and the like can produce more softer, less rigid,and more flexible invention gel.

Because of the (E) midblocks, the invention gels of the inventionexhibit different physical characteristics and improvements oversubstantially amorphous gels including damage tolerance, improved crackpropagation resistance, improved tear resistance producing knotty tearsas opposed to smooth tears, crystalizable melting point of 28° C.,improved resistance to fatigue, higher hysteresis, etc. Moreover, theinvention gels when stretched exhibit additional yielding as shown bynecking caused by stress induced crystallinity. Additionally, thecrystallization rates of the crystalizable midblocks can be controlledand slowed depending on thermal history producing time delay recoveryupon deformation.

Regarding resistance to fatigue, fatigue (as used herein) is the decayof mechanical properties after repeated application of stress andstrain. Fatigue tests give information about the ability of a materialto resist the development of cracks or crazes resulting from a largenumber of deformation cycles. Fatigue test can be conducted bysubjecting samples of amorphous and invention gels to deformation cyclesto failure (appearance of cracks, crazes, rips or tears in the gels).

Tensile strength can be determined by extending a selected gel sample tobreak as measured at 180° U bend around a 5.0 mm mandrel attached to aspring scale. Likewise, tear strength of a notched sample can bedetermined by propagating a tear as measured at 180° U bend around a 5.0mm diameter mandrel attached to a spring scale.

Various block copolymers can be obtained which are amorphous, highlyrubbery, and exhibiting minimum dynamic hysteresis.

Block Copolymer S-EB-S

The monomer butadiene can be polymerized in a ether/hydrocarbon solventto give a 50/50 ratio of 1,2 poly(butadiene)/1,4 poly(butadiene) and onhydrogenation no long runs of —CH₂— groups and negligible crystallinity,ie, about (0.5)⁴ or 0.06 or 6% and actual crystallinity of about 3%. Dueto the constraints of Tg and minimum hysteresis, conventional S-EB-Shave ethylene-butylene ratios of about 60:40 with a crystallinity ofabout (0.6)⁴ or 0.129 or 12% and actual crystallinity of about 7.7%.

Block Copolymer S-EP-S

The monomer isoprene when polymerized will produce 95% 1,4poly(isoprene)/15% 3,4 poly(isoprene) and upon hydrogenation will formamorphous, rubbery poly(ethylene-propylene) midblock and no long runs of—CH₂— and no crystallinity.

Mixed Block Copolymer S-EB/EP-S

The polymerization of a 50/50 mixture of isoprene/butadiene monomers insuitable ether/hydrocarbon solvents to give equal amounts of 1,2 and 1,4poly(butadiene) on hydrogenation will produce a maximum crystallinity of(0.25)⁴ or 0.4%. The actual crystallinity would be approximately about0.2%, which is negligible and results in a good rubbery midblock.

The polymerization of a 80/20 mixture of isoprene/butadiene monomers insuitable ether/hydrocarbon solvents to give equal amounts of 1,2 and 1,4poly(butadiene) will upon hydrogenation produce a low crystallinity of(0.10)⁴ or 0.01%. The actual crystallinity would be approximately about0.006%, which is negligible and results in a good rubbery midblock.

The polymerization of a 20/80 mixture of isoprene/butadiene monomers insuitable ether/hydrocarbon solvents to give equal amounts of 1,2 and 1,4poly(butadiene) will upon hydrogenation produce a low crystallinity of(0.4)⁴ or 2.56%. The actual crystallinity would be approximately about1.53%, which is negligible and results in a good rubbery midblock.

The polymerization of a 20/80 mixture of isoprene/butadiene monomers insuitable ether/hydrocarbon solvents to give a 40:60 ratio of 1,2 and 1,4poly(butadiene) will upon hydrogenation produce a low crystallinity of(0.48)₄ or 5.3%. The actual crystallinity would be approximately about3.2%, which is negligible and results in a good rubbery midblock.

For purpose of convince and simplicity, the hydrogenated polybutadieneare denoted as follows: -E- denotes 85% R-1 units, -B- denotes 70% R-2units, -EB- denotes between 15 and 70% R-2 units, -EBn- denotes n % R-2units, and -EP- denotes 90% R-3 units.

Table 1 below gives the % of units on hydrogenation ofpolybutadiene/polyisoprene copolymer midblock where n is the mole %polybutadiene in the polybutadiene-polyisoprene starting polymer

n = R-1 R-2 R-3 R-4 0% 0% 0% 95% 5% 20% 18% 2% 76% 4% 40% 36% 4% 57% 3%60% 54% 6% 38% 2% 80% 72% 8% 19% 1% 100% 90% 10% 0% 0%

Therefore, the percentage that can crystallize is [(—CH₂—)₄]₄ since thisis the chance of getting four (—CH₂—)₄ units in sequence. The percentagethat will crystallize is about 60% of this.

n = (—CH₂—)₄ [(—CH₂—)₄]₄ 0.6 X [(—CH₂—)₄]_(n) 0% 0%   0%   0% 20% 18%0.1% 0.06%  40% 36% 1.7% 1.0% 60% 54% 8.5% 5.1% 80% 72% 26.9%  16.1% 100% 90% 65.6%  39.4% This applies to polymerization in a hydrocarbon solvent. In an ether(eg, diethylether), the percentage (—CH₂—)₄ units will be reduced sothat crystallinity will be negligible.

n = (—CH₂—)₄ [(—CH₂—)₄]₄ 0.6X [(—CH₂—)₄]_(n) 0% 0%   0%   0% 20% 5%0.0006%  0.0004%  40% 10% 0.01% 0.006%  60% 15% 0.05% 0.03% 80% 20%0.16% 0.10% 100% 25% 0.39% 0.23%

These values are all negligible. There will be no detectablecrystallinity in any of these polymer midblocks. In a mixedether/hydrocarbon solvent, values will be intermediate, depending on theratio of ether to hydrocarbon.

The midblocks (Z) of one or more -E-, -B-, -EB-, or -EP- can comprisevarious combinations of midblocks between the selected end blocks (A);these include: -E-EB-, -E-EP-, -B-EP-, -B-EB-, -E-EP-E-, -E-EB-B-,-B-EP-B-, -B-EB-B-, -E-B-EB-, -E-B-EP-, -EB-EP-, -E-EB-EP-, -E-EP-EB-,-B-EB-EP-, -B-EP-EB-, -E-EP-E-EP-, -E-EP-E-EB-, -B-EP-B-EP-,-B-EB-B-EB-, -B-EB-B-EP-, -E-EB-B-EP-, -E-EP-B-EB-, -E-EP-E-EP-E-,-B-EP-B-EP-B-, -E-EP-E-EB-, -E-EP-E-EP-EB-, -E-EP-E-EP-E-,-E-EP-EB-EP-EB-B- and the like.

The (i) and (v) block copolymers of (A-Z-A) can be obtained bysequential or random synthesis methods followed by hydrogenation of themidblocks. As denoted above, abbreviations are interchangeably used, forexample, (S-E-EP-S) denotespoly(styrene-ethylene-ethylene-co-propylene-styrene). Other linear blockcopolymers (denoted in abbreviations) include the following: (S-E-EB-S),(S-E-EP-S), (S-B-EP-S), (S-B-EB-S), (S-E-EP-E-S), (S-E-EB-B-S),(S-B-EP-B-S), (S-B-EB-B-S), (S-E-B-EB-S), (S-E-B-EP-S), (S-EB-EP-S),(S-E-EB-EP-S), (S-E-EP-EB-S), (S-B-EB-EP-S), (S-B-EP-EB-S),(S-E-EP-E-EP-S), (S-E-EP-E-EB-S), (S-EP-B-EP-S), (S-B-EB-B-EB-S),(S-B-EB-B-EP-S), (S-E-EB-B-EP-S), (S-E-EP-B-EB-S), (S-E-EP-E-EP-E-S),(S-B-EP-B-EP-B-S), (S-E-EP-E-EB-S), (S-E-EP-E-EP-EB-S),(S-E-EP-E-EP-E-S), (S-E-EP-EB-EP-EB-B-S), (S-E-EP-EB-EP-EB . . . -S) andthe like.

The (ii) and (iv) multiblock star-shaped (or radial) copolymers(A-Z)_(n)X can be obtained by sequential synthesis methods includinghydrogenation of selected block copolymers made by polymerizing half ofthe block copolymers such as SBS or SIS and couple the halves with acoupling agent such as an organic dihalide; or couple with an agent suchas SnCl₄, which results in star-shaped block copolymers (four branches).Coupling with divinyl benzene give block copolymers which are veryhighly branched. Radial block copolymers suitable for use in forming theinvention gels of the present invention include: (S-E-EB-S)_(n),(S-E-EP)_(n), (S-B-EP)_(n), (S-B-EB)_(n), (S-E-EP-E)_(n),(S-E-EB-B)_(n), (S-B-EP-B)_(n), (S-B-EB-B)_(n), (S-E-B-EB)_(n),(S-E-B-EP)_(n), (S-EB-EP)_(n), (S-E-EB-EP)_(n), (S-E-EP-EB)_(n),(S-B-EB-EP)_(n), (S-B-EP-EB)_(n), (S-E-EP-E-EP)_(n), (S-E-EP-E-EB)_(n),(S-EP-B-EP)_(n), (S-B-EB-B-EB)_(n), (S-B-EB-B-EP)_(n),(S-E-EB-B-EP)_(n), (S-E-EP-B-EB)_(n), (S-E-EP-E-EP-E)_(n),(S-B-EP-B-EP-B)_(n), (S-E-EP-E-EB)_(n), (S-E-EP-E-EP-EB)_(n),(S-E-EP-E-EP-E)_(n), (S-E-EP-EB-EP-EB-B)_(n)

The selected amount of crystallinity in the midblock should besufficient to achieve improvements in one or more physical propertiesincluding improved damage tolerance, improved crack propagationresistance, improved tear resistance, improved resistance to fatigue ofthe bulk gel and resistance to catastrophic fatigue failure of inventiongel s, such as between the surfaces of the invention gel and substrateor at the interfaces of the interlocking material(s) and invention gel,which improvements are not found in amorphous gels at corresponding gelrigidities.

As an example, when fabric interlocked or saturated with amorphousS-EB-S gels (gel s) are used as gel liners for lower limb or above theknee prosthesis to reduce pain over pressure areas and give relief tothe amputee, the commonly used amorphous gels forming the liners cantear or rip apart during marathon racewalk after 50–70 miles. Inextended use, the amorphous gels can rip on the bottom of the liner innormal racewalk training of 40–60 miles over a six weeks period. In suchdemanding applications, the invention gels are especially advantageousand is found to have greater tear resistance and resistance to fatigueresulting from a large number of deformation cycles than amorphous gels.The invention gels are also useful for forming various orthotics andprosthetic articles such as for lower extremity prosthesis of the L5664(lower extremity socket insert, above knee), L5665 (socket insert,multi-durometer, below knee), L5666 (below knee, cuff suspensioninterface), L5667 (below knee, above knee, socket insert, suctionsuspension with locking mechanism) type devices as described by theAmerican Orthotic & Prosthetic Association (AOPA) codes. The inventiongels are useful for making AOPA code devices for upper extremityprosthetics. The devices can be cast molded or injection molded incombination with or without fiber or fabric backing or fiber or fabricreinforcement. When such liners are made without fabric backing, variousgels can be used to form gel-gel and gel-gel-gel s and the like withvarying gel rigidities for the different gel layer(s). Such liners canbe made from high viscosity SEBS (such as Kraton 1651 and Septon 8006)and moderate viscosity SEBS (Kraton 1654 and Septon 8007) blockcopolymers gels. The add advantage of liners made from SEEPS gels isthat such gels exhibit tear and fatigue resistance not achievable usingSEBS and SEPS alone.

Silipos product catalogue (referenced above) which shows a Single SockGel Liner product #1272, This and other same but different sizedproducts (#1275 and #1276) were on Public sale. Products #1272 wasoffered for public sale and sold to the public on or about Jan. 31,1995, #1275 was on public sale on or about Jan. 31, 1995, and #1276 wason public scale on or about Dec. 31, 1994. The Single Sock Gel Liner isa tube sock-shaped covering for enclosing an amputation stump with aopen end for introduction of the stump and a closed end opposite theopen end. The liner is a fabric in the shape of a tube sock coated ononly one side with a gel made from a block copolymer and oil. The gelliners products #1272, #1275, and #1276 were on public sale as of theabove mentioned dates which products were coated with a block copolymergel described in U.S. Pat. Nos. 4,369,284 and 4,618,213.

Selected linear block and radial copolymers utilized in forming theinvention gels of the invention are characterized as having an ethyleneto butylene midblock ratio (E:B) of about 85:15 to about 65:35.Advantageously, the butylene concentration of the midblock is about 35%or less, more advantageously, about 30% or less, still moreadvantageously, about 25% or less, especially advantageously, about 20%or less. Advantageously, the ethylene to butylene midblock ratios canrange from and in between about 89:11, 88:12, 87:13, 86:14, 85:15,84:16, 83:17, 82:18, 81:19, 80:20, 79:21, 78:22, 77:23, 76:24, 75:25,74:26, 73:27, 72:28, 71:29, 70:30, 69:31, 68:32, 67:33, 66:34 to about65:35.

The A to Z midblock ratio of the block copolymers suitable for forminginvention gels of the invention can range from about 20:80 to 40:60 andhigher. More specifically, the values can be and in between: 15:85,19:81, 20:80, 21:79, 22:78, 23:77, 24:76, 25:75, 26:74, 27:73, 28:72,29:71, 30:70, 31:69, 32:68, 33:67, 34:66, 35:65, 36:64, 37:63, 38:62,39:61, 40:60, 41:59, 42:58, 43:57, 44:65, 45:55, 46:54, 47:53, 48:52,49:51, 50:50, 51:49, 52:48, 53:47, 54:46, 55:45, 56:44, 57:43, 58:42,59:41, 60:40, 61:39, 62:38, 63:37, 64:36, 65:35, 66:34, 6:33, 68:32,69:31, 70:30 and higher.

The invention gels can be made in combination with or without a selectedamount of one or more selected polymers and copolymers in amountswithout substantially decreasing the desired properties. Such polymersincludes: thermoplastic crystalizable polyurethane elastomers withhydrocarbon blocks, homopolymers, copolymers, block copolymers,polyethylene, polypropylene, polystyrene, polyethylene copolymers,polypropylene copolymers, and the like. Other (vii) polymers andcopolymers can be linear, star-shaped (radial), branched, or multiarm;these including: (SBS) styrene-butadiene-styrene block copolymers, (SIS)styrene-isoprene-styrene block copolymers, low and medium viscosity(S-EB-S) styrene-ethylene-butylene-styrene block copolymers, (S-EP)styrene-ethylene-propylene block copolymers, (S-EP-S)styrene-ethylene/propylene-styrene block copolymers, (S-E-EPS)styrene-ethylene-ethylene/propylene-styrene block copolymers, (SB)_(n)styrene-butadiene and (S-EB)_(n), (S-EB-S)_(n), (S-E-EP)_(n), (SEP)_(n),(SI)_(n) multi-arm, branched or star-shaped copolymers,polyethyleneoxide (EO), poly(dimethylphenylene oxide), teflon (TFE,PTFE, PEA, FEP, etc), optical clear amorphous copolymers based on2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole (PDD) andtetrafluoroethylene (TFE), maleated S-EB-S block copolymer,polycarbonate, ethylene vinyl alcohol copolymer, ethylene/styreneinterpolymers, and the like. Still, other polymers include homopolymerswhich can be utilized in minor amounts; these include: polystyrene,polydimethylsiloxane, polyolefins such as polybutylene, polyethylene,Hoechst Celanese/PEG 20000 UHMW polyethylene (Mw=1,000,000–6,000,000),polyethylene copolymers, polypropylene, silicone (Tospearl 120A, 145Aetc) and the like. Polyurethane thermoplastic crystalizable copolymerswith hydrocarbon midblocks based on saturated hydrocarbon diols(Handlin, D., Chin. S., and Masse. M., et al. “POLYURETHANE ELASTOMERSBASED ON NEW SATURATED HYDROCARBON DIOLS” Published Society of PlasticsIndustry, Polyurethane Division, Las Vegas, Oct. 23, 1996) are alsosuitable for use in blending with the block copolymers (i–vi) used informing the invention gels of the invention. Such saturated hydrocarbondiols include hydroxyl terminated oligomers of poly(ethylene-butylene)(EB), poly(ethylene-propylene) (EP), -E-EB-, -E-EP-, -B-EP-, -B-EB-,-E-EP-E-, -E-EB-B-, -B-EP-B-, -B-EB-B-, -E-B-EB-, -E-B-EP-, -EB-EP-,-E-EB-EP-, -E-EP-EB-, -B-EB-EP-, -B-EP-EB-, -E-EP-E-EP-, -E-EP-E-EB-,-B-EP-B-EP-, -B-EB-B-EB-, -B-EB-B-EP-, -E-EB-B-EP-, -E-EP-B-EB-,-E-EP-E-EP-E-, -B-EP-B-EP-B-, -E-EP-E-EB-, -E-EP-E-EP-EB-,-E-EP-E-EP-E-, -E-EP-EB-EP-EB-B- and the like. As an example,thermoplastic polyurethane made with isocyanates and chain extenderssuch as TMPD and BEPD from saturated hydrocarbon diol KLP L-2203 havinga hard segment contents of 22% exhibits clean phase separation of thehard and soft segments with glass a transition of −50° C. KLP L-2203based TPU's can be mixed with the crystalizable block copolymers to formsoft invention gels within the gel rigidity ranges of the invention.

As described in U.S. Patent Application 20020061982 and incorporatedherein by reference, ethylene/styrene interpolymers are prepared bypolymerizing i) ethylene or one or more alpha-olefin monomers and ii)one or more vinyl or vinylidene aromatic monomers and/or one or moresterically hindered aliphatic or cycloaliphatic vinyl or vinylidenemonomers, and optionally iii) other polymerizable ethylenicallyunsaturated monomer(s).

Ethylene/styrene interpolymers can be substantially random,psuedo-random, random, alternately, diadic, triadic, tetradic or anycombination thereof. That is, the interpolymer product can be variablyincorporated and optionally variably sequenced. Preferredethylene/styrene interpolymers are substantially random ethylene/styreneinterpolymers.

The high glassy component (viii) copolymers suitable for use in formingthe invention gels of the invention include high styrene componentBASF's Styroflex series copolymers including BX 6105 with a statisticalSB sequence for the low elastomeric segments (styrene to butadiene ratioof 1:1) and an overall styrene content of almost 70%, high styrenecontent Shell Kraton G, Kraton D-1122X (SB)_(n), D-4122 SBS, D-4240(SB)_(n), D-4230 (SB)_(n), DX-1150 SBS, D-4140 SBS, D-1115 SBS, D-4222SBS, Kraton D-1401P, SEBS, Dexco's Vector 6241-D, 4411-D, Fina'sFinaclear high styrene content SBS series copolymers, PhillipsPetroleum's XK40 K-Resin styrene/butadiene copolymers, Kuraray's S2104SEPS. The (viii) copolymers include amorphous polymers with high styrenecontent: SBS, SIS, SEPS, SEB/EPS, and the like. The (i–viii) copolymerswith glassy to elastomeric ratios can range from and in between 37:63,37.6:62.4, 38:62, 39:61, 40:60, 41:59, 42:58, 43:57, 44:65, 45:55,46:54, 47:53, 48:52, 49:51, 50:50, 51:49 52:48, 53:47, 54:46, 55:45,56:44, 57:43, 58:42, 59:41, 60:40, 6:39, 62:38, 63:37, 64:36, 65:35,66:34, 67:33, 68:32, 69:31, 70:30, 7:29, 72:28, 73:27, 74:26, 75:25,76:24, 77:23, 78:22, 79:21, to 80:20 and higher.

Suitable polyolefins include polyethylene and polyethylene copolymerssuch as Dow Chemical Company's Dowlex 3010, 2021D, 2038, 2042A, 2049,2049A, 2071, 2077, 2244A, 2267A; Dow Affinity ethylene alpha-olefinresin PL-1840, SE-1400, SM-1300; more suitably: Dow Elite 5100, 5110,5200, 5400, Primacor 141-XT, 1430, 1420, 1320, 3330, 3150, 2912, 3340,3460; Dow Attane (ultra low density ethylene-octene-1 copolymers) 4803,4801, 4602, Eastman Mxsten CV copolymers of ethylene and hexene(0.905–0.910 g/cm3).

The conventional term “major” means about 51 weight percent and higher(e.g. 55%, 60%, 65%, 70%, 75%, 80% and the like) and the term “minor”means 49 weight percent and lower (e.g. 2%, 5%, 10%, 15%, 20%, 25% andthe like).

Representative plasticizer oil gels (polymer+oil) of the inventioninclude: (a) Kraton G 1651, G 1654X gels; (b) Kraton G 4600 gels; (c)Kraton G 4609 gels; other suitable high viscosity polymer and oil gelsinclude: (d) Tuftec H 1051 gels; (e) Tuftec H 1041 gels; (f) Tuftec H1052 gels; (g) Kuraray SEEPS 4055 gel; (h) Kuraray SEBS 8006 gel; (i)Kuraray SEPS 2005 gel; (j) Kuraray SEPS 2006 gel, and (k) Gels made fromblends (polyblends) of (a)–(b) with other polymers and copolymersinclude: (1) SEBS-SBS gels; (2) SEBS-SIS gels; (3) SEBS-(SEP) gels; (4)SEBS-(SEB)_(n) gels; (5) SEBS-(SEB)_(n) gels; (6) SEBS-(SEP)_(n) gels:(7) SEBS-(SI)_(n) gels; (8) SEBS-(SI) multiarm gels; (9) SEBS-(SEB)_(n)gels; (10) (SEB)_(n) star-shaped copolymer gels; (11) gels made fromblends of (a)–(k) with other homopolymers include: (12) SEBS/polystyrenegels; (13) SEBS/polybutylene gels; (14) SEBS/polyethylene gels; (14)SEBS/polypropylene gels; (16) SEP/SEBS oil gels (17), SEP/SEPS oil gels(18), SEP/SEPS/SEB oil gels (19), SEPS/SEBS/SEP oil gels (20), SEB/SEBS(21), EB-EP/SEBS (22), SEBS/EB (23), SEBS/EP (24), (25) (SEB)_(n) gels,(26) (SEP)_(n) gels, (27) SEEPS gels, and the like.

Representative examples of commercial elastomers that can be formed withplasticizing oils in combination with the high viscosity triblock andbranched copolymers described above into suitable gels for use in makingthe gel compositions and articles of the invention: Shell Kratons D1101,D1102, D1107, D1111, D1112, D1113X, D1114X, D1116, D1117, D1118X,D1122X, D1125X, D1133X, D1135X, D1184, D1188X, D1300X, D1320X, D4122,D4141, D4158, D4240, G1650, G1652, G1657, G1701X, G1702X, G1726X,G1750X, G1765X, FG1901X, FG1921X, D2103, D2109, D2122X, D3202, D3204,D3226, D5298, D5999X, D7340, G1654X, G2701, G2703, G2705, C1706, G2721X,G7155, G7430, G7450, G7523X, G7528X, G7680, G7705, G7702X, G7720,G7722X, G7820, G7821X, G7827, G7890X, G7940. Kuraray's SEEPS, SEP/SEPSor SEP/SEB/SEPS Nos. 1001, 1050, 2002, 2003, 3023, 2007, 2043, 2063,2050, 2103, 2104 (SEPS with a high styrene content of 65), 2105, 4033(SEEPS), 4044 (SEEPS), 4045 (SEEPS), 4077 (SEEPS), 4099 (SEEPS), 8004(SEBS), 8007, H-VS-3 (S-V-EP)n, Dexco polymers (Vector): 4411, 4461,6241, DPX555, tuftec-P series SBBS (styrene-butadiene-butylene-styrene)and the like.

The Kuraray SEPTON 4000 (SEEPS) series block polymers: 4033, 4044, 4055,4045, 4077, 4099, and the like useful in making the gels of the instantinvention are made from hydrogenated styrene isoprene/butadiene styreneblock copolymer or more specifically made from hydrogenated styreneblock polymer with 2-methyl-1,3-butadiene and 1,3-butadiene. Suchpoly(styrene-isoprene/butadiene-styrene) polymers, depending on thebutadiene structure, when hydrogenated will result in “(SEB/EPS)”. Incases where the butadiene structures are controlled, it is appropriateto denote (SEB/EPS) as (SE/EPS) where E/EP isethylene-ethylene-propylene or more simply as (SEEPS) to indicate thatthe ethylene (E) of the ethylene-butylene (EB) segment of the midblock(EB/EP) of the (SEB/EPS) block polymer is substantially greater thanbutylene (B) and the amount of (E) can be sufficient so as to exhibitethylene crystallinity. As indicated below, it is the presence orabsence of the styrene methyl group which can be use to distinguish theSEBS polymer from the SEPS and SEEPS types of polymer. The SEEPS polymerof the invention gel, within the experimental uncertainty, lackssufficient butylene. The invention gels can comprise (I) SEEPS polymersand other (II) polymers, such as: SEPS, SEBS, SIS, SBS, SEB/EPS and thelike.

As taught in my co-pending applications: Ser. Nos. 10/273,828 and10/199,9364, and specifically incorporated herein, the unusualproperties of the invention SEEPS gels can be attributed to alteringdifferent phase or interfacial arrangements of the domains of themultiblock copolymers. The presence of polyethylene and crystallinity inblock copolymers can be determined by NMR and DSC.

Physical measurements (NMR and DSC) of typical commercial Kraton G 1651,Septon 2006, Septon 4033 and Septon 4055 block were performed. Two typesof ¹³C NMR spectra data were collected. The gated decoupled experimentprovided quantitative data for each type of carbon atom. The DEPTexperiment identified each type of carbon atom having attached protons.The DEPT data allowed assignment of the resonances in the gateddecoupled experiment, which was then integrated for quantitation of thedifferent types of midblock and end groups in each polymer tested

The relative quantities of each type of carbon group in the variouspolymers were found. The uncertainty associated with these measurementsis estimated as ±3 percentage units. Only the Kraton 1651 spectrum hadresonances below about 20 ppm. These resonances, at 10.7–10.9 ppm, wereassigned to the butylene methyl group and distinguish the SEBS polymerfrom the SEPS and SEEPS types of polymer (36). Only the Septon 2006spectrum lacked the resonance at about 20 ppm that is characteristic ofpolyethylene units (defined here as three contiguous CH₂ groups), andthis feature distinguishes the SEPS polymer from the SEBS and SEEPSpolymers (49). There were additional differences between the spectra.The Septon 2006 and the Septon 4033 and 4055 spectra all showedresonances at 20 ppm, whereas the spectrum of Kraton 1651 was missingthis resonance. The 20 ppm peak is characteristic of the methyl group ofa propylene subunit, which is present in SEPS and SEEPS polymers butabsent in the SEBS polymer. There were also a methylene peak, at 24.6ppm, and a methine peak at 32.8 ppm, in all of the Septon spectra butnot in the Kraton 1651 spectra. These resonances also arise from thepropylene subunit.

The chemical shifts, relative intensities, and relative integrationswere the same for the spectra of the Septon 4033 and Septon 4053,indicating that these two polymeric compositions are identical based onNMR spectroscopy.

DSC of ASTM D3417-99 was modified to provide conditions for the samplesto have the best possible chance to exhibit any crystallinity. Theprotocol was as follows: (1) heat to 140° C. @ 10° C./min., (2) cool to0° C. @ 2° C./min., (3) place in freezer for 1 week, (4) heat to 140° C.@ 1° C./min, and (5) cool to 0° C. @ 1° C./min.

This protocol was used with the exception that the samples were left inthe freezer for approximately 2 months, instead of 1 week, because theDSC equipment broke during the week after the first run and requiredsome time for repair. This delay is not expected to have negativelyimpacted the results of the experiment.

Two HDPE reference samples gave clearly defined crystallizationexotherms and fusion endotherms, allowing calculation of heats ofcrystallization and fusion. These results showed that the equipment andmethodology were fully functional, and this check was performed dailyduring DSC operation. Of the samples, only Kraton 1651 showeddiscernable transitions for both crystallization and fusion. The Septon2006 showed no discernable transitions, which is consistent with itsSEPS structure being entirely amorphous. The Septons 4033 and 4055showed crystallization exotherms.

The heats of crystallization for the Kraton 1651 and Septons 4033 and4055 were small, below about 3 J/g, indicating that small amounts ofcrystallinity are present in these polymers. The DSC data show:

Kraton 1651: crystallization exotherm peak at 18.09° C., crystallizationexotherm—mass normalized enthalpy (J/g) of 1.43, fusion endortherm peakat 34.13° C., and Fusion Endotherm—mass normalized enthalphy J/g of15.17.

Septon 2006: crystallization exotherm peak (not detected),crystallization exotherm—mass normalized enthalpy (not detected), fusionendortherm peak NONE, and Fusion Endotherm—mass normalized enthalphy(not detected).

Septon 4033: crystallization exotherm peak at 2.86° C. crystallizationexotherm—mass normalized enthalpy (J/g) of 3.00, fusion endortherm peak(not detected), and Fusion Endotherm—mass normalized enthalphy (notdetected).

Septon 4055: crystallization exotherm peak at 14.4° C. crystallizationexotherm—mass normalized enthalpy (J/g) of 1.32, fusion endortherm peak(not detected), and Fusion Endotherm—mass normalized enthalphy (notdetected).

Aldrich 13813JU polyethylene reference: crystallization exotherm peak at119.72° C., crystallization exotherm—mass normalized enthalpy (J/g) of174.60, fusion endortherm peak at 130.70° C., and Fusion Endotherm—massnormalized enthalphy J/g of 189.90.

The invention gels made from higher viscosity SEEPS copolymers (I) areresistant to breaking when sheared than SEPS triblock copolymer gels.This can be demonstrated by forming a very soft gel, for example 100parts copolymer to 800 parts plasticizing oil. The soft gel is cut intoa strip of 2.5 cm×2.5 cm cross-section, the gel strip is grippedlengthwise tightly in the left hand about its cross-section and anexposed part of the gel strip being gripped lengthwise around itscross-section tightly by the right hand as close to the left band aspossible without stretching. With the two hands gripping the gel strip'scross-section, the hands are moved in opposite directions to shear apartthe gel strip at its cross-section. The shearing action by the grippinghands is done at the fastest speed possible as can be performed by humanhands. The shearing action is performed at a fraction of a second,possible at about 0.5 seconds. Using this demonstration, the SEEPScopolymer (I) invention gels will not easily break completely apart aswould gels formed from SEPS triblock copolymers. In some cases, it willtake two, three, or more attempts to shear a high viscosity copolymer(I) gel strip this way. Whereas, a lower viscosity triblock copolymergel strip can be sheared apart on the first try. For gels made fromcopolymers with viscosities of 5 wt % solution in Toluene of from lessthan 2 mPa-S to 500 mPa-S and higher, their shear resistance willdecrease with decreasing viscosity.

Hence, it is the selected SEEPS which provides the improved tear andfatigue resistance of the invention gel compositions and articles. SEEPSgels of corresponding rigidity exhibit improved greater tear and greaterfatigue resistance over SEPS gels and SEBS gels.

As taught in my co-pending applications: Ser. Nos. 09/721,213;09/130,545; 10/273,828; 09/517,230; 09/412,886; 10/199,9364 andspecifically incorporated herein, tear strength and resistance tofatigue of the high viscosity SEEPS gels of the invention atcorresponding rigidities are found to be greater than that of SEPS gels.Greater tear and fatigue resistance is also found when SEEPS gels aremade in combination with other (II) polymers, such as SEPS, SEBS, SBS,SIS, low viscosity SEBS, lower viscosity SEEPS, PS, PE, PP, (SI)_(n),(SB)_(n), (SEB)_(n), Ashai SB/EBSpoly(styrene-butadiene-ethylene-butylene-styrene), and the like.

The amorphous S-EB-S and (S-EB)_(n) copolymers can have a broad range ofstyrene to ethylene-butylene ratios (S:EB) of about 20:80 or less toabout 40:60 or higher. The S:EB weight ratios can range from lower thanabout 20:80 to above about 40:60 and higher. More specifically, thevalues can be from and in between: 15:85, 19:81, 20:80, 21:79, 22:78,23:77, 24:76, 25:75, 26:74, 27:73, 28:72, 29:71, 30:70, 31:69, 32:68,33:67, 34:66, 35:65, 36:64, (and higher ratios for viii copolymers)37:63, 37.6:62.4, 38:62, 39:61, 40:60, 41:59, 42:58, 43:57, 44:65,45:55, 46:54, 47:53, 48:52, 49:51, 50:50, 51:49 52:48 and etc. Otherratio values of less than 19:81 or higher than 51:49 are also possible.Broadly, the styrene block to elastomeric block ratio of the highviscosity liner and star copolymers is about 20:80 to about 40:60 orhigher, less broadly about 31:69 to about 40:60, preferably about 32:68to about 38:62, more preferably about 32:68 to about 36:64, particularlymore preferably about 32:68 to about 34:66, especially more preferablyabout 33:67 to about 36:64, and still more preferably about 30:70.

The Brookfield Viscosity of a 5 weight percent solids solution intoluene at 30° C. of 2006, 4033, 4045, 4055, and 4077 typically rangeabout 20–35, about 25–150, about 60–150, about 200–400 respectively.Typical Brookfield Viscosities of a 10 weight percent solids solution intoluene at 30° C. of 1001, 1050, 2007, 2063, 2043, 4033, 2005, 2006, areabout 70, 70, 17, 29, 32, 50, 1200, and 1220 respectively. TypicalBrookfield Viscosity of a 25 weight percent solids solution in tolueneat 25° C. of Kraton D1101, D1116, D1184, D1300X, G1701X, G1702X areabout 4000, 9000, 20000, 6000, 50000 and 50000 cps respectively. TypicalBrookfield Viscosity of a 10 weight percent solids solution in tolueneat 25° C. of G1654X is about 370 cps. The Brookfield Viscosities of a 20and 30 weight percent solids solution in toluene at 30° C. of H-VS-3 areabout 133 cps and 350 cps respectively.

Suitable block copolymers and their typical viscosities are furtherdescribed. Shell Technical Bulletin SC: 1393–92 gives solution viscosityas measured with a Brookfield model RVT viscometer at 25° C. for KratonG 1654X at 10% weight in toluene of approximately 400 cps and at 15%weight in toluene of approximately 5,600 cps. Shell publication SC:68–79gives solution viscosity at 25° C. for Kraton G 1651 at 20 weightpercent in toluene of approximately 2,000 cps. When measured at 5 weightpercent solution in toluene at 30° C., the solution viscosity of KratonG 1651 is about 40. Examples of high viscosity S-EB-S triblockcopolymers includes Kuraray's S-EB-S 8006 which exhibits a solutionviscosity at 5 weight percent at 30° C. of about 51 cps. Kuraray's 2006SEPS polymer exhibits a viscosity at 20 weight percent solution intoluene at 30° C. of about 78,000 cps, at 5 weight percent of about 27cps, at 10 weight percent of about 1220 cps, and at 20 weight percent78,000 cps. Kuraray SEPS 2005 polymer exhibits a viscosity at 5 weightpercent solution in toluene at 30° C. of about 28 cps, at 10 weightpercent of about 1200 cps, and at 20 weight percent 76,000 cps. Othergrades of S-EB-S, SEPS, (SEB)_(n), (SEP)_(n) polymers can also beutilized in the present invention provided such polymers exhibits therequired high viscosity. Such S-EB-S polymers include (high viscosity)Kraton G 1855X which has a Specific Gravity of 0.92, BrookfieldViscosity of a 25 weight percent solids solution in toluene at 25° C. ofabout 40,000 cps or about 8,000 to about 20,000 cps at a 20 weightpercent solids solution in toluene at 25° C.

The styrene to ethylene and butylene (S:EB) weight ratios for the Shelldesignated polymers can have a low range of 20:80 or less. Although thetypical ratio values for Kraton G 1651, 4600, and 4609 are approximatelyabout 33:67 and for Kraton G 1855X approximately about 27:73, Kraton G1654X (a lower molecular weight version of Kraton G 1651 with somewhatlower physical properties such as lower solution and melt viscosity) isapproximately about 31:69, these ratios can vary broadly from thetypical product specification values. In the case of Kuraray's S-EB-Spolymer 8006 the S:EB weight ratio is about 35:65. In the case ofKuraray's 2005 (SEPS), and 2006 (SEPS), the S:EP weight ratios are 20:80and 35:65 respectively. The styrene to ethylene-ethylene/propylene(S:EB-EP) ratios of Kuraray's SEPTON 4033, 4045, 4055, and 4077 aretypically about 30, 37.6, 30, 30 respectively. More typically the(S:EB-EP) and (S:EP) ratios can vary broadly much like S:EB ratios ofS-EB-S and (SEB)_(n) from less than 19.81 to higher than 51:49 (asrecited above) are possible. It should be noted that multiblockcopolymers including SEPTON 4033, 4044, 4045, 4055, 4077, 4099 and thelike are described in my cited copending parent applications and are thesubject matter of related inventions.

The block copolymers such as Kraton G 1654X having ratios of 31:69 orhigher can be used and do exhibit about the same physical properties inmany respects to Kraton G 1651 while Kraton G 1654X with ratios below31:69 can also be use, but they are less advantageous due to theirdecrease in the desirable properties of the final gel.

Plasticizers particularly advantageous for use in practicing the presentinvention are will known in the art, they include rubber processing oilssuch as paraffinic and naphthenic petroleum oils, highly refinedaromatic-free paraffinic and naphthenic food and technical grade whitepetroleum mineral oils, and synthetic liquid oligomers of polybutene,polypropene, polyterpene, etc. The synthetic series process oils arehigh viscosity oligomers which are permanently fluid liquid nonolefins,isoparaffins or paraffins of moderate to high molecular weight.

Selected amounts of any compatible plasticizers can be utilized informing the invention gels of the invention, but because of the non-tackproperty of the invention gels of the invention, the major amount ofplasticizers used should be low viscosity plasticizers havingviscosities advantageously of not greater than about 30 cSt @ 40° C.

Examples of representative commercially available plasticizing oilsinclude Amoco® polybutenes, hydrogenated polybutenes, polybutenes withepoxide functionality at one end of the polybutene polymer, liquidpoly(ethylene/butylene), liquid hetero-telechelic polymers ofpoly(ethylene/butylene/styrene) with epoxidized polyisoprene andpoly(ethylene/butylene) with epoxidized polyisoprene: Example of suchpolybutenes include: L-14 (320 Mn), L-50 (420 Mn), L-100 (460 Mn), H-15(560 Mn), H-25 (610 Mn), H-35 (660 Mn), H-50 (750 Mn), H-100 (920 Mn),H-300 (1290 Mn), L-14E (27–37 cst @ 100° F. Viscosity), H-300E (635–690cst @ 210° F. Viscosity), Actipol E6 (365 Mn), E16 (973 Mn), E23 (1433Mn), Kraton L-1203, EKP-206, EKP-207, HPVM-2203 and the like. Example ofvarious commercially oils include: ARCO Prime (55, 70, 90, 200, 350, 400and the like). Duroprime and Tufflo oils (6006, 6016, 6016M, 6026, 6036,6056, 6206, etc), other white mineral oils include: Bayol, Bernol,American, Drakeol, Ervol, Gloria, Kaydol, Litetek, Lyondell (Duroprime55, 70, 90, 200, 350, 400, Ideal FG 32, 46, 68, 100, 220, 460), Marcol,Parol, Peneteck, Primol, Protol, Sontex, and the like. Oils useful inthe invention gel include: Witco 40 oil, Ervol, Benol, Blandol,Semtol-100, Semtol 85, Semtol 70, Semtol 40, Orzol, Britol, Protol,Rudol, Carnation, Klearol; 350, 100, 85, 70, 40, Pd-23, Pd 25, Pd28, FG32, 46, 68, 100, 220, 460, Duroprime Ds-L, Ds-M, Duropac 70, 90, Crystex22, Af-L, Af M, 6006, 6016, 6026, Tufflo 6056, Ste Oil Co, Inc:Invention Plus 70, 200, 350, Lyondell: Duroprime DS L & M. Duropac 70,90, Crystex 22, Crystex AF L & M, Tufflo 6006, 6016; Chevron TexacoCorp: Superta White Oil 5, Superta 7, 9, 10, 13, 18, 21, 31, 35, 38, 50,Penreco: Conosol 340, Conosol C-200, Drakeol 15, 13, 10, 10B, 9, 7, 5,50, Peneteck, Ultra Chemical Inc, Ultraol White 60Nf, Ultraol White50Nf, Witco Hydrobrite 100, 550, 1000, and the like.

Selected amounts of one or more compatible plasticizers can be used toachieve gel rigidities of from less than about 2 gram Bloom to about1,800 gram Bloom and higher. Tack may not completely be dependent uponthe amount of the glassy phase, by using selected amount of certain lowviscosity oil plasticizers, block copolymers of SEBS, SEEPS, SEPS,SEP_(n), SEB_(n), and the like, gel tack can be reduced or the gel canbe made non-tacky.

Major or minor amounts (based on 100 parts by weight of base elastomer)of any compatible second plasticizers can be utilized in forming theinvention gel, but because of the non-tack property of the inventiongel, the major amount of first plasticizers used should be low viscosityplasticizers having viscosities advantageously of not greater than about30 cSt @ 40° C., for example values and in between: 30, 29, 28, 27, 26,25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7,6, 5, 4, 3 and the like. Such low viscosity plasticizers arecommercially available as, for example, from Witco: Rudol, Ervol, Benol,Blandol, Carnation, Klearol, Semtol100, Semtol 85, Semtol 70, Semtol 40;from Lyondell: Duroprime 55, 70, 90, Duroprime DS L & M, Duropac 70, 90,Crystex 22, Crystex AF L & M, Tufflo 6006, 6016 and the like. Theinvention gel tack decreases with decreasing oil viscosities of fromabout 30 to 3. Invention gels which are non-tacky to the touch can beachieved using oils with viscosities of about 10 cSt @ 40° C. and less.Best result can be achieved using oils with viscosities of about 6 andless. Oils of higher viscosities of from about 500 cSt @ 40° C. to about30 produce higher and higher tack with increase in viscosities. Heattemperature set resistance improves with increase in oil viscosity. Oilswith viscosities less than about 15 exhibit heat set at about 50° C.Therefore a combination of low viscosity oils to improve low tack andhigh viscosity oils to improve set can be achieved by blending variousoils having the desired viscosities for the desired end use. Thedisassociation of polystyrene is about 100° C. to about 135° C., theinvention gels do not melt below the disassociation temperature ofpolystyrene. It is important that fishing bait when stored in a fishingbox in the hot Sun at about 50° C. to about 58° C. do not suffersubstantial heat set as tested at these temperatures in a 108° U bendfor one hour.

It has been found that the lower the oil viscosity, the lower the heatset of the resulting gel composition and the higher the oil viscosityuse in the gel compositions of the invention, the higher the heat set ofthe resulting gel composition. For example, if the first plasticizer isless than about 50 SUS @ 100° F., the heat set of the resulting gelcomposition comprising 100 parts of (I) copolymers of equal parts ofSEEPS 4055 and Kraton G 1651 with about 600 parts by weight of the firstplasticizer, the resulting is found to have a heat set less than that ofa conventional PVC plastisol fishing bait at about 50° C. However, asthe 50 Vis SUS @ 100° F. oil of the formulation is gradually replacedwith a higher viscosity oil of about 80–90 SUS @ 100° C., the heat setdeformation improves with increasing amounts of the higher viscosityoil. In order to obtain equal heat set performance as conventional PVCplastisol fishing bait, the first and second plasticizers would have tobe of equal amounts in the gel composition. Replacing the firstplasticizer with a greater amount would increase the gel tack. If tackis not of great concern, then a higher amount of the second plasticizerswould be beneficial for improving heat set at higher and highertemperatures to the point that the second plasticizers can reach greaterthan 2525 SUS @ 100° C. (Ideal FG 100, 220, or 460 oil) the resultinggel composition would not exhibit set at even temperatures greater than400° F.

The cited first plasticizers with or without one or more secondplasticizers can be used in sufficient amounts to achieve a gel rigidityof from about 20 gram Bloom to about 1,800 gram Bloom. The secondplasticizers in effective amounts in combination with the firstplasticizers can provide a greater temperature compression set than agelatinous composition having the same rigidity formed from the firstplasticizers alone. The second plasticizers when used can provide agreater temperature compression set than a gelatinous composition havingthe same rigidity formed from the first plasticizers alone or formedfrom a combination of the first plasticizers and the secondplasticizers. The first plasticizers being in effective amounts withsaid second plasticizers can provide a Gram Tack lower than a gelatinouscomposition having the same rigidity formed from the second plasticizersalone.

Generally, plasticizing oils with average molecular weights less thanabout 200 and greater than about 700 may also be used (e.g. H-300 (1290Mn)). It is well know that minor and sufficient amounts of Vitamin E isadded to the described commercially available oils during bulkprocessing which is useful as a oil stabilizer, antioxidant, andpreservative.

Of all the factors, the amount of plasticizing oils can be controlledand adjusted advantageously to obtain substantially higher tear andtensile strength gels. The improvements in tensile strength of theinvention gels are accompanied by corresponding increase in gel rigidityas the amount of plasticizing oils are lowered until the rigidity of theinvention gels becomes much higher than that of the gums which surroundthe teeth. Although higher tensile strengths can be obtained as theamount of plasticizing oils in the gel approaches zero, the tensilestrength of the floss, however, must be maintained at an acceptable gelrigidity (at sufficient high plasticizing oil levels) in order to be assoft as the gums required for flossing. For example, the rigidities of agel containing 100, 200, or 300 parts by weight of oil is much higherthan a gel containing 300, 400, 500, 600, 800, or 900 parts of oil.

These gels can exhibit a larger unit lateral contraction at the sameelongation per unit of length as their counterpart parent gels fromwhich the invention gels are derived or formed. This property wouldallow a same unit volume of gel when elongated as its parent to easilywedge between the teeth when flossing. It would seem that a gel havingthe 1.0 cm³ volume made from a ratio of 100 parts by weight of copolymerand 400 parts plasticizer would have a unique macro volumeconfigurations that is at equilibrium with the plasticizer which is muchlike a 3-D fingerprint which is uniquely different from any other gel ofa different copolymer to plasticizer ratio. Reducing the plasticizercontent of a ratio 100:400 gel to a 100:300 ratio of copolymer toplasticizer will decrease the amount of plasticizer, but the originalmacro volume configurations will remain the same.

Speculative theories not withstanding, configurations may take the formof (1) swiss cheese, (2) sponge, (3) the insides of a loaf of bread, (4)structures liken to ocean brain corals, (5) large structures and smallstructures forming the 3-D gel volume landscape, (6) the outer heatedsurface which cools faster than the inner volumes of the gel during itscooling histories may have a patterned crust (rich in A micro-phases)like that of a loaf of bread and the inner volume may have much like1–5, and (7) the many different possible structures are unlimited andvolume landscapes may be interconnected at the macro-level by threads ormicro-strands of Z micro-phases.

The amount of plasticizer extracted can advantageously range from lessthan about 10% by weight to about 90% and higher of the total weight ofthe plasticizer. More advantageously, the extracted amounts ofplasticizer can range from less than about 20% by weight to about 80% byweight of the total plasticizer, and still more advantageously, fromabout 25% to about 75%. Plasticizing oils contained in the inventiongels can be extracted by any conventional methods, such as solventextraction, physical extraction, pressure, pressure-heat, heat-solvent,pressure-solvent-heat, vacuum extraction, vacuum-heat extraction,vacuum-pressure extraction, vacuum-heat-pressure extraction,vacuum-solvent extraction, vacuum-heat-solvent-pressure extraction, etc.The solvents selected, should be solvents which do not substantiallydisrupt the A and Z phases of the (I) copolymers forming the inventiongels. Any solvent which will extract plasticizer from the gel and do notdisrupt the A and Z phases can be utilized. Suitable solvents includealcohols, primary, secondary and tertiary alcohols, glycols, etc.,examples include methanol, ethanol, tetradecanol, etc. Likewise, thepressures and heat applied to remove the desired amounts of oils shouldnot be sufficient to disrupt the A and Z domains of the (I) copolymers.To form a lower rigidity gel, the simplest method is to subject the gelto heat in a partial vacuum or under higher vacuum for a selected periodof time, depending on the amount of plasticizer to be extracted.

Surprisingly, as disclosed in my application U.S. Ser. No. 09/896,047filed Jun. 30, 2001, oil extraction from the invention gels can beachieved with little or no energy in the presence of one or moresilicone fluids to almost any degree. A theory can be made to explainthe physics involved in the extraction process which reasoning is asfollows: (1) When water is placed in contact with an oil extended gel,the gel will not over time exhibit weight loss. (2) When oil is add to acolumn of water in a test tube, the oil will separate out and find itslevel above the column of water. (3) The surface tension of water at 25°C. is about 72.0 mN/m. (4) The surface tension of oil (mineral oil) at25° C. is about 29.7 mN/m. (5) The surface tension of silicone fluid at25° C. range from about 16 to abut 22 mN/m (for example: the surfacetension of 100 cSt silicone fluid at STP is 20.9 mN/m). (6) The densityof oil is less than the density of silicone fluid, silicone grease,silicone gel, and silicone elastomer. (7) Oil is not a polar liquid andis highly compatible with the rubber phase of the oil gel formingpolymer. (8) Silicone is polar and not compatible with the polymer'srubber phase.

The molecules of a liquid oil drop attract each other. The interactionsof an oil molecule in the liquid oil drop are balanced by an equalattractive force in all directions. Oil molecules on the surface of theliquid oil drop experience an imbalance of forces at the interface withair. The effect is the presence of free energy at the surface. Thisexcess energy is called surface free energy and is quantified as ameasurement of energy/area. This can be described as tension or surfacetension which is quantified as a force/length measurement or m/Nm.

Clearly gravity is the only force pulling on the extracted oil from thegel in the presence of silicone fluid at the gel-petri dish interface inthe examples below. In the case of gel samples in the petri dishes incontact with silicone fluids, the extracted oil are collected on the topsurface layer of the silicone fluid while the silicone fluid maintainconstant contact and surrounds the gel sample. In the case of gel placedin a test tube of silicone fluid of different viscosity, the oil isextracted and migrates and collect at the top of the silicone fluidsurface while the gel reduces in volume with time. The oil extractionprocess in silicone is accompanied by buoyant forces removing theextracted oil from the surroundings of the gel constantly surroundingthe gel with fresh silicone fluid while in the example of alcohol, sincethe oil is heavier, the oil is maintained and surrounds the gel sampleforming a equilibrium condition of oil surround the gel sample whilekeeping the alcohol from being in contact with the gel sample. Thereforein order to use alcohol to extract oil from a gel sample, the extractedoil must be constantly removed from the oil alcohol mixture as is thecase during soxhlet extraction which process requires additional energyto pump the oil-alcohol mixture away from the sample and removing theoil before forcing the alcohol back to the gel sample surface to performfurther extraction.

Silicone fluid is efficient and useful for extracting oil form oil gelcompositions with the assistance of gravity and buoyancy of oil in thesilicone fluids.

It is very difficult to extract, separate, or remove oil from an oil gelcomposition by positive or vacuum pressure or heat while using little orno energy and because of the affinity of the rubber midblock for oil,not even the weight of a two ton truck resting on a four square footarea (placing a layer of gel between four pairs of one foot squareparallel steel plates one set under each of the truck tire resting onthe gels) can separate the oil from the gel composition.

The use of silicone fluids of various viscosity acts as a liquid semiporous membrane when placed in constant contact with an oil gelcomposition will induce oil to migrate out of the gel composition. Bythe use of gravity or oil buoyancy, no energy is required run the oilextraction process.

In the case of the invention gels of this application made in the shapeof a fishing bait in contact with silicone fluid, the elastomer orrubber being highly compatible with the oil, holds the oil in placewithin the boundary of the rubber molecular phase. It is this affinityof the (i) rubber and oil molecules and (ii) the attraction of oilmolecules for each other that prevents the oil from bleeding out of thesurface of the gel body. There exist then, at the surface of the gelseveral types of surface tensions of: (iii) oil-air surface tension,(iv) oil-rubber surface tension, (v) rubber-air surface tension, (vi)rubber/oil-air surface tension, and (vii) rubber-rubber surface tension.Other forces acting on the gel are: the elastic force of the polymernetwork pulling inwards, similar to stretched out rubber bands, which isin equilibrium with the oil molecules' attraction to the rubbermolecules of the polymer network. In the case of SBS, the lowercompatibility of the midblock butadiene with oil, once a gel is made,the SBS network immediately contracts due to elastic forces to produceoil bleeding which is evidence of the poor compatibility of the rubberblock for the oil molecules.

The intermolecular forces that bind similar molecules together arecalled cohesive forces. Intermolecular forces that bind a substance to asurface are called adhesive forces.

When two liquids are in contact such as oil and silicone fluid, there isinterfacial tension. The more dense fluid is referred to herein as the“heavy phase” and the less dense fluid is referred to as the “lightphase”. The action at the surface of the oil extended polymer gelsurface when brought into contact with silicone fluid is as follows: adrop of silicone fluid when placed on the flat surface of a oil extendedpolymer gel will wet the gel surface and spread over a larger area ascompared to a drop of oil placed on the same gel surface. Because thesurface free energy of the silicone fluid in contact with the gelsurface is lower than the surface free energy of the oil, the siliconefluid has the ability to displaces the oil from the surface of the gel.

The invention gels can optionally comprise selected major or minoramounts of one or more polymers or copolymers (III) provided the amountsand combinations are selected without substantially decreasing thedesired properties. The polymers and copolymers can be linear,star-shaped, branched, or multiarm; these including: (SBS)styrene-butadiene-styrene block copolymers, (SIS)styrene-isoprene-styrene block copolymers, (low styrene content SEBSsuch as Kraton 1650 and 1652) styrene-ethylene-butylene-styrene blockcopolymers, (SEP) styrene-ethylene-propylene block copolymers, (SEPSKraton RP-1618) styrene-ethylene-propylene-styrene block copolymers,(SB)_(n) styrene-butadiene and (SEB)_(n), (SEBS)_(n), (SEP)_(n),(SI)_(n) styrene-isoprene multi-arm, branched or star-shaped copolymers,polyethyleneoxide (EO), poly(dimethylphenylene oxide) and the like.Still, other (III) polymers include homopolymers which can be utilizedin minor amounts; these include: polystyrene, polybutylene,polyethylene, polypropylene and the like.

In the case of high molecular weight and combination of high styrenecontent of the block copolymer which may be the reason for improve tearand fatigue resistance, these properties may be achieved and maintainedby blending (I) copolymers of SEEPS with (III) copolymers of SBS (KratonD 1101, 1144, 1116, 1118, 4141, 4150, 1133, 1184, 4158, 1401P, 4240, andKX219), SEBS (G1651, 1654).

Other (III) polymers useful in the invention gels include: oftrifluoromethyl-4,5-difuoro-1,3-dioxole and tetrafluoroethylene,polytetrafluoroethylene, maleated poly(styrene-ethylene-butylene),maleated poly(styrene-ethylene-butylene)n, maleatedpoly(styrene-ethylene-butylene-styrene), maleatedpoly(styrene-ethylene-propylene)n, maleatedpoly(styrene-ethylene-propylene-styrene), poly(dimethylphenylene oxide),poly(ethylene-butylene), poly(ethylene-propylene),poly(ethylene-styrene) interpolymer made by metallocene catalysts, usingsingle site, constrained geometry addition polymerization catalysts,poly(styrene-butadiene), poly(styrene-butadiene)n,poly(styrene-butadiene-styrene), poly(styrene-ethylene-butylene),poly(styrene-ethylene-butylene)n,poly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-propylene), poly(styrene-ethylene-propylene)n,poly(styrene-ethylene-propylene-styrene), poly(styrene-isoprene),poly(styrene-isoprene)n, poly(styrene-isoprene-styrene),poly(styrene-isoprene-styrene)n, polyamide, polybutylene, polybutylene,polycarbonate, polydimethylsiloxane; polyethylene vinyl alcoholcopolymer, polyethylene, polyethyleneoxide, polypropylene, polystyrene,polyvinyl alcohol, wherein said selected copolymer is a linear, radial,star-shaped, branched or multiarm copolymer, wherein n is greater thanone

When the selected (III) polymers and copolymers contain greater glassyblock of styrene content of 33 and higher, such may be effective toprovide a Gram Tack lower than a gelatinous composition having the samerigidity formed from the (I) block copolymers and corresponding firstplasticizers alone or the first plasticizers with a second plasticizers.The selected component (III) polymers of polystyrene forming a styrenecontent of 33 and higher when used in effective amounts may provide agreater temperature compression set than a gelatinous composition havingthe same rigidity formed from the (I) block copolymers and correspondingfirst plasticizers alone or the first plasticizers with a secondplasticizer.

On the other hand, the lower viscosity first plasticizer can impartlower Gram Tack to the invention gels than an increase of styrenecontent of the (I) copolymers or (III) polymers and copolymers. The lowtack and non tacky invention gels can be made from one or more linear,branched, star-shaped (radial), or multiarm block copolymers or mixturesof two or more such block copolymers having one or more midblock polymerchains which invention gels have use as articles with high tearpropagation resistance. The invention gels also possess high tensilestrength and rapid return from high extension and can exist in analtered state of delay elastomeric recovery as it regains its originalshape following high extensions or dynamic deformations. The inventiongels also exhibit low set, high dimensional stability, crack, tear,craze, and creep resistance, excellent tensile strength and highelongation, long service life under shear, stress and strain and capableof withstanding repeated dynamic shear, tear and stress forces,excellent processing ability for cast molding, extruding, fiber formingfilm forming and spinning, non-toxic, nearly tasteless and odorless,soft and strong, optically clear, highly flexible, possessing elasticmemory, substantially with little or no plasticizer bleedout, and havinglow or no tack in contact with human hand which reduction in tackinesscan be measured. The non tacky and optical properties of the inventiongels do not rely on powders or surface activation by additives toestablish their non-tackiness. The invention gels' non-tackinesspervasive the gels' entire bulk or volume. No matter how deep or inwhich direction a cut is made, the invention gels are non tackythroughout (at all points internally as well as on the gels' surface).Once the gel is cut, the invention gel immediately exhibitsnon-tackiness at its newly cut surface. Hence, the homogeneity of thenon-tackiness and optical properties of the invention gels are notknown.

Because of their improved tear resistance and resistance to fatigue, thegel compositions and s of the invention including the fluffy inventiongels disclosed in U.S. Ser. No. 08/984,459 (incorporated above byreference) exhibit versatility as materials formed into hollowed thickwall body shapes for use in deep sea ice water diving or insulating thebody from extreme cold. The fluffy invention gels are advantageouslyuseful for making one layer gloves for vibration damping which preventsdamage to blood capillaries in the fingers and hand caused by handlingstrong shock and vibrating equipment. Of great advantage are theunexpanded particulate materials which can be dispersed and within acontrolled temperature heating range can produce a predetermined volumeof closed cell particulate dispersions forming the fluffy gels. Theparticulate materials useful are unexpanded microspheres ofpoly(acrylonitrile-methacrylonitrile) copolymers encapsulated liquidisopentane which are available from Akzo Nobel by the tradenameExpancel. The thermoplastic microspheres comprises about 80% weight ofcopolymer and about 6 to about 16% isopentane and are furthercharacterized as having a unexpanded relative density of about 1.2(H₂O=1.0), particle size of about 3 to about 50 microns, a T_(start) orsofting temperature of about 106° C. to about 135° C. and adecomposition or rupturing temperature T_(max) of about 138° C. to about195° C. The unexpanded thermoplastic microspheres are activated by heatand expand to approximately about 50 times its unexpanded size toprovide an average particle density of about less than 0.020 specificgravity. Their lowest calculated density reached at T_(max) during TMAtest is between about 0.25 to about 0.017 g/cm³. More specifically,unexpanded grades of microspheres include grades followed by (range oftemperatures T_(start)° C./T_(max)° C.): #051 (106–111/138–147), #053(95–102/137–145), #054 (125–135/140/150), #091 (118–126/161–171),#091-80 (118–126/171–181), and #092-120 (118–126/185–195).

The invention gels can be casted molded, pressured molded, injectionmolded and various methods of forming gel articles and with or withoutinterlocking with various substrates, such as open cell materials,metals, ceramics, glasses, and plastics, elastomers, fluropolymers,expanded fluropolymers, Teflon (TFE, PTFE, PEA, FEP, etc), expandedTeflon, spongy expanded nylon, etc.; the molten invention gel isdeformed as it is being cooled. Useful open-cell plastics include:polyamides, polyimides, polyesters, polyisocyanurates, polyisocyanates,polyurethanes, poly(vinyl alcohol), etc. Suitable open-celled Plastic(sponges) are described in “Expanded Plastics and Related Products”,Chemical Technology Review No. 221, Noyes Data Corp., 1983, and “AppliedPolymer Science”, Organic Coatings and Plastic Chemistry, 1975. Thesepublications are incorporated herein by reference.

The instant gel compositions and s including fluffy gels are excellentfor cast, injection, or spinning molding and the molded products havehigh tear resistance characteristics which cannot be anticipated formthe properties of the raw components. Other conventional methods offorming the composition can be utilized. The invention gel compositionsand s including fluffy gel articles can be formed by blending, injectionmolding, extruding, spinning, casting, dipping and other conventionalmethods. For example, Shapes having various cross-section can beextruded. The fluffy invention gels can also be formed directly intoarticles or remelted in any suitable hot melt applicator and extrudedinto shaped articles and films or spun into threads, strips, bands,yarns, or other shapes.

Comparisons of oil extended S-EB-S triblock copolymers have beendescribed in Shell Chemical Company Technical Bulletin SC: 1102–89(April 1989) “KRATON® THERMOPLASTIC RUBBERS IN OIL GELS” which isincorporated herein by reference.

The stearic acid and microcrystalline wax components of the gelsdescribed in my earlier U.S. Pat. No. 5,760,117 are non-sticky,invention and non-adhering. The non-adhering gels containing additivessuch as stearic acid and the like, however, feels greasy due theadditive's high solubility in oil and low melting points forming agreasy coating on the surface of the gel. The inherently invention gelswhich are an improvement over the greasy feeling gels of U.S. Pat. No.5,760,117 described above, although feels non-adhering and completelynon-tacky and non-greasy, can exhibit a high coefficient of friction orhigh COF.

I have also found that by incorporating sufficient amounts of one ormore of a selected (high melting, low oil soluble, and polar) low COFagents (such as polyphenolics with one or more sterically hinderedphenolic hydroxyl groups) in the gels will result in the appearance oflarge crystals in the interior as well as on the surface of the gels.Such crystals are shown in FIG. 5 (top view) photo of the top of ainvention gel article with phenolic crystals. These crystals have noeffect on the high COF of the resulting gels. Contrary to the combinedeffects of stearic acid and microcrystalline wax, the presence ofmicrocrystalline wax with polyphenolic in gels does not lessen the gel'sCOF and have little effect on reducing the size of the largepolyphenolic crystals. Likewise the crystallinity and glassy componentsby themselves can not by themselves reduce the inherent high COF ofthese gels. Consequently, gels containing microcrystalline wax andpolyphenolics exhibit high COF.

Surprisingly, when selected amounts of internal nucleating agents areincorporated in the gels in combination with selected amounts of one ormore of a low COF agents, the large crystals no longer forms within thegels; and the surface of the gels exhibit lower and lower COF with time.Bringing the gels in contact with selected external nucleating agentsdecreases the time or totally eliminates the time needed for the gel'souter surface to exhibit a low COF.

The gels and soft elastomers incorporating low COF agents and internaland/or external nucleating agents exhibit a much lower coefficient offriction when measured in contact with a reference surface than gels andsoft elastomers made without such components.

School book physics teaches COF can be determined experimentally, fortwo given surfaces that are dry and not lubricated, the ratio of thetangential force needed to overcome the friction to the normal forcewhich holds the two surfaces in contact (e.g., the weight of a block ofgel or elastomer material on a surface) is a constant, independent ofthe area or of the velocity with which the surfaces (surface of a sideof the block in contact with another surface) move over wide limits.This ratio is μ, the coefficient of friction. The coefficient of slidingfriction for a block of material beingμ=(f/F _(n))where f is the force of friction, and F_(n) the normal force. For thecase of the block on the horizontal table, if m is the mass of theblock, then mg is the normal force and the above equation can be writtenasμ=f/mg.In the case the block of a block rests on a board, originallyhorizontal, and that the board then is tilted until a limiting angle φis reached, beyond which the block will begin to slide down the board.At this angle the component of the weight of the object along the boardis just equal in amount to that necessary to overcome the force offriction. The force down the plane is mg sin φ, while the normal forceis mg cos φ. Therefore we haveμ=(mg sin φ)/(mg cos φ) or μ=tan φ.

The limiting value of φ for which μ=tan φ is true is call the angle ofrepose. Measurement of the tangent of this angle will give thecoefficient of friction of the contacting surfaces of the block and theboard that slide one upon the other.

As an example of low COF agents advantageously useful in softthermoplastic elastomers and gels, excellent results is achieved with 50grams of a polyphenolic with sterically hindered phenolic hydroxylgroups (Irganox 1010), about 100 grams of one or more nucleating agents(such as very fine particle size sodium benzoate, dibenzylidenesorbitol, its alkylated derivatives, talc, zinc sterate, amorphoussilica, aluminum sterate, etc.) and 5,000 grams of S-EB-S and 25,000gram of oil. The same excellent result is achieved when S-EB-S isadjusted to 3,000 grams, 4,000 grams, etc. The same result is achievedwith copolymers as well as in combination with other polymers. Moreover,when about 50 grams of tetrakis[methylene3,-(3′5′-di-tertbutyl-4″-hydroxyphenyl)propionate]methane is use (perabout 22.68 Kilograms or 50 lbs of gel) as a low COF agent, tack iscompletely removed from the surface of the gel after two to three weeksof blooming.

When this is repeated with an external nucleating agent, such as withvarious fine particles for coating the outside surface of the elastomeror gel, such as with talc, calcium stearate, zinc sterate, amorphoussilica, aluminum sterate, fine flour, corn starch, fine soil, fine sand,fine metallic powder, vacuum dust, fine wood dusts and the like, lowerCOF is achieved within a few days to less than several hours. Aftercoating the gel for the desired period of time, the fine polar and watersoluble particles can be washed off with water and soap, while non-polarand non-water soluble fine powders can be removed by wearing it off orby lifting it off with the use of adhesive tapes if so desired. FIG. 6(top view) photo of the top of a invention gel article made withphenolics and external nucleating agents.

What is the surface properties of low CFO agents at theair/plasticizer-copolymer interface? Theory notwithstanding, theresulting gel surface will comprise of very fine molecular segments oreven very fine invention grains of low COF agents confined at theair/plasticizer and polymer interface. Depending on concentration, thenon-polar segments of the low COF agents will have a tendency of beingadsorpted by the predominate plasticizer and copolymer midblock phase atthe gel surface. The slightly polar or more polar segments of the lowCOF agents are adsorbed to a lesser extent by the plasticizer-copolymersurface. This is supported by observing the water wettingcharacteristics at the gel surface with and with out low COF agents atthe air gel surface interface. A drop of water will bead up and notreadily wet the gel surface free of any low COF agents (hydrophobic).The presence of even slightly polar low COF agents exposed on thesurface of the gel will make a drop of water flatten out and not bead upwhen place on the gel surface (hydrophilic).

Commercial high melting point, low oil solubility, and polar low COFagents such as polyphenolics which are advantageously useful in thepresent invention include: Ethanox 330 (Ethyl), Irganox 1010(Ciba-Geigy), Santechhem A/O 15-1 (Santech), Ultra 210 (GE), Hostanox 03(Hoechst Celanese), Irganox 3114 (Ciba-Geigy), Mixxim AO-3 (Fairmont),and the like. Other high melting point, low oil solubility, polar lowCOF agents contemplated are common amino acids: Such As Alamine,Arginine, Asparagine, Aspartic Acid, Cysteine, Glutamine, Glutamic Acid,Glycine, Histidine, Isoleucine, Leucine, Lysine, Methionine,Phenylalanine, Proline, Serine, Threonine, Tryptophan, Tyrosine andValine. The melting points of these amino acids range from about 178° C.to about 344° C. The amino acids having greater advantage serving as lowCOF agents are Asparagine, Aspartic acid, Glutamine, Glutamic acid,Tryptophan, and Tyrosine

Copolymer for forming the low COF compositions include block copolymers,random copolymers, metallocene catalyzed ethylene-styrene copolymers,Low COF invention gels made from thermoplastic elastomer copolymers andblock copolymers having one or more crystalizable polyethylene segmentsor midblocks. The low COF invention gels advantageously exhibit high,higher, and higher, and ever higher tear resistance than realized beforeas well as improved high tensile strength. The low COF invention gelsalso exhibit improved damage tolerance, crack propagation resistance andespecially improved resistance to high stress rupture which combinationof properties makes the gels advantageously and surprisingly suitablefor use as toys, inflatable air cushions in automobiles, and the like.

The invention gels of this invention are advantageously useful formaking low COF gel compositions. Moreover, various polymer gels madefrom linear triblock copolymers, multi-arm block copolymers, branchedblock copolymers, radial block copolymers, multiblock copolymers,random/non-random copolymers, thermoplastic crystalline polyurethanecopolymers with hydrocarbon midblocks or mixtures of two or more of suchcopolymers can also be made with low COF. The COF values of theinvention gels formed form the low COF and nucleating agents are foundto be about less than 1, more advantageously less than 0.7, moreadvantageously less than 0.577, still more advantageously less than0.466 and still more advantageously less than 0.40. The low COFinvention gels of the invention can range from less than 1.0 to aboutless than 0.40.

As taught in my application Ser. No. 08/289,690 filed Aug. 11, 1994, nowU.S. Pat. No. 5,633,286 and specifically incorporated herein, additivesuseful in the gel of the present invention include: tetrakis[methylene3,-(3′5′-di-tertbutyl-4″-hydroxyphenyl)propionate]methane, octadecyl3-(3″,5″-di-tert-butyl-4″-hydroxyphenyl)propionate,distearyl-pentaerythritol-diproprionate, thiodiethylenebis-(3,5-ter-butyl-4-hydroxy)hydrocinnamate,(1,3,5-trimethyl-2,4,6-tris[3,5-di-tert-butyl-4-hydroxybenzyl]benzene),4,4″-methylenebis(2,6-di-tert-butylphenol), stearic acid, oleic acid,stearamide, behenamide, oleamide, erucamide, N,N″-ethylenebisstearamide,N,N″-ethylenebisoleamide, sterryl erucamide, erucyl erucamide, oleylpalmitamide, stearyl stearamide, erucyl stearamide, calcium sterate,other metal sterates, waxes (e.g. polyethylene, polypropylene,microcrystalline, carnauba, paraffin, montan, candelilla, beeswax,ozokerite, ceresine, and the like). The gel can also contain metallicpigments (aluminum and brass flakes), TiO2, mica, fluorescent dyes andpigments, phosphorescent pigments, aluminatrihydrate, antimony oxide,iron oxides (Fe3O4, —Fe2O3, etc.), iron cobalt oxides, chromium dioxide,iron, barium ferrite, strontium ferrite and other magnetic particlematerials, molybdenum, silicone fluids, lake pigments, aluminates,ceramic pigments, ironblues, ultramarines, phthalocynines, azo pigments,carbon blacks, silicon dioxide, silica, clay, feldspar, glassmicrospheres, barium ferrite, wollastonite and the like. The report ofthe committee on Magnetic Materials, Publication NMAB-426, NationalAcademy Press (1985) is incorporated herein by reference.

The invention gels can also be made into s. The invention gels can becasted unto various substrates, such as open cell materials, metals,ceramics, glasses, and plastics, elastomers, fluropolymers, expandedfluropolymers, Teflon (TFE, FTFE, PEA, FEP, etc), expanded Teflon,spongy expanded nylon, etc.; the molten invention gel is deformed as itis being cooled. Useful open-cell plastics include: polyamides,polyimides, polyesters, polyisocyanurates, polyisocyanates,polyurethanes, poly(vinyl alcohol), etc. Suitable open-celled Plastic(sponges) are described in “Expanded Plastics and Related Products”,Chemical Technology Review No. 221, Noyes Data Corp., 1983, and “AppliedPolymer Science”, Organic Coatings and Plastic Chemistry, 1975. Thesepublications are incorporated herein by reference.

The invention gels are prepared by blending together the componentsincluding other additives as desired at about 23° C. to about 100° C.forming a paste like mixture and further heating said mixture uniformlyto about 150° C. to about 200° C. until a homogeneous molten blend isobtained. Lower and higher temperatures can also be utilized dependingon the viscosity of the oils and amounts of multiblock copolymers andpolymer used. These components blend easily in the melt and a heatedvessel equipped with a stirrer is all that is required. Small batchescan be easily blended in a test tube using a glass stirring rod formixing. While conventional large vessels with pressure and/or vacuummeans can be utilized in forming large batches of the invention gels inamounts of about 40 lbs or less to 10,000 lbs or more. For example, in alarge vessel, inert gases can be employed for removing the compositionfrom a closed vessel at the end of mixing and a partial vacuum can beapplied to remove any entrapped bubbles. Stirring rates utilized forlarge batches can range from about less than 10 rpm to about 40 rpm orhigher.

The gel compositions can also be formed directly into articles orremelted in any suitable hot melt applicator and extruded or spun intothreads, bands, or other shapes. The instant compositions is excellentfor cast molding and the molded products have various excellentcharacteristics which cannot be anticipated form the properties of theraw components. Other conventional methods of forming the compositioncan be utilized.

As taught in my application Ser. No. 08/288,690 filed Aug. 11, 1994, nowU.S. Pat. No. 5,633,286 and specifically incorporated herein, thegelatinous elastomer composition of the invention is excellent forforming the gelatinous elastomer articles of the invention. Thegelatinous elastomer articles can be formed by blending, melting,dipping, casting, injection molding, extruding and other conventionalmethods. For example, a foam of a preselected pore size can be placed ina mold cavity and a preselected amount of a preselected rigidity ofgelatinous elastomer composition is then injected into the mold. Themold is allow to cool to room temperature and the article removed. Apreselected rigidity of molten gelatinous elastomer composition can becast directly onto a section of open cell foam to form the article.Likewise, an article of foam can be dipped into a preselected rigidityof molten gelatinous elastomer composition and re-dipped into the sameor different composition of a different rigidity. The shaped article ofthe invention can be conventionally covered with protective skins ofelastomeric film, fabric or both as needed.

The composition can also be remelted in any suitable hot melt applicatorfor hot dipping, extrusion, sputtering, or spraying on to the foams orsponges so as to form the gelatinous elastomer articles of theinvention.

As taught in my application Ser. No. 08/288,690 filed Aug. 11, 1994, nowU.S. Pat. No. 5,633,286 and specifically incorporated herein, generallythe molten gelatinous elastomer composition will adhere sufficiently tocertain plastics (e.g. acrylic, ethylene copolymers, nylon,polybutylene, polycarbonate, polystyrene, polyester, polyethylene,polypropylene, styrene copolymers, and the like) provided thetemperature of the molten gelatinous elastomer composition is sufficienthigh to fuse or nearly fuse with the plastic. In order to obtainsufficient adhesion to glass, ceramics, or certain metals, sufficienttemperature is also required (e.g. above 250° F.). Commercial resinswhich can aid in adhesion to materials (plastics, glass, and metals) maybe added in minor amounts to the gelatinous elastomer composition, theseresins include: Super Sta-tac, Nevtac, Piccotac, Escorez, Wingtack,Hercotac, Betaprene, Zonarez, Nirez, Piccolyte, Sylvatac, Foral,Pentalyn, Arkon P, Regalrez, Cumar LX, Picco 6000, Nevchem, Piccotex,Kristalex, Piccolastic, LX-1035, and the like. The conventional term“major” means about 51 weight percent and higher (e.g. 55%, 60%, 65%,70%, 75%, 80% and the like) and the term “minor” means 49 weight percentand lower (e.g. 2%, 5%, 10%, 15%, 20%, 25% and the like to less than50%)(based on 100 parts of (I)).

For example, Shapes having various cross-section can be extruded. Theinvention gels can also be formed directly into articles or remelted inany suitable hot melt applicator and extruded into shaped articles andfilms or spun into threads, strips, bands, yarns, or other shapes. Withrespect to various shapes and yarn, its size are conventionally measuredin denier (grams/9000 meter), tex (grams/1000 meter), and gage (1/2.54cm). Gage, tex, denier can be converted as follows:tex=denier/9=specific gravity (2135/gage), for rectangular crosssection, tex=specific gravity (5806×103)(th)(w)/9, where th is thethickness and w the width of the strip, both in centimeters. Generaldescriptions of (1) block copolymers, (2) elastomeric fibers andconventional (3) gels are found in volume 2, starting at pp. 324–415,volume 6, pp 733–755, and volume 7, pp. 515 of ENCYCLOPEDIA OF POLYMERSCIENCE AND ENGINEERING, 1987 which volumes are incorporated herein byreference.

The invention gels are excellent for cast molding and the moldedproducts have various excellent characteristics which cannot beanticipated form the properties of the raw components. Otherconventional methods of forming the composition can be utilized.

Not only do the invention gels have all the desirable combination ofphysical and mechanical properties substantially similar to highviscosity amorphous S-EB-S gels such as high elongation at break of1,600%, ultimate tensile strength of about 8×10⁵ dyne/cm² and higher,low elongation set at break of substantially not greater than about 2%,substantially about 100% snap back when extended to 1,200% elongation,and a gel rigidity of substantially from about 2 gram to about 1,800gram Bloom and higher, the invention gels of the present inventionexhibit improved tear resistance and resistance to fatigue notobtainable from amorphous S-EB-S gels at corresponding gel rigidities.

The invention gels of the present invention exhibit one or more of thefollowing properties. These are: (1) tensile strength of about 8×10⁵dyne/cm² to about 10⁷ dyne/cm² and greater; (2) elongation of less thanabout 1,600% to about 3,000% and higher; (3) elasticity modules of about10⁴ dyne/cm² to about 106 dyne/cm² and greater; (4) shear modules ofabout 10⁴ dyne/cm² to about 106 dyne/cm² and greater as measured with a1, 2, and 3 kilogram load at 23° C.; (5) gel rigidity of about less thanabout 2 gram Bloom to about 1,800 gram Bloom and higher as measured bythe gram weight required to depress a gel a distance of 4 mm with apiston having a cross-sectional area of 1 square cm at 23° C.; (6) tearpropagation resistance greater than the tear resistance of amorphousS-EB-S gels at corresponding gel rigidities; (7) resistance to fatiguegreater than the fatigue resistance of amorphous S-EB-S gels atcorresponding gel rigidities; (8) and substantially 100% snap backrecovery when extended at a crosshead separation speed of 25 cm/minuteto 1,200% at 23° C. Properties (1), (2), (3), and (6) above are measuredat a crosshead separation speed of 25 cm/minute at 23° C.

The invention gel articles molded from the invention gels haveadditional important advantages in that they end-use performanceproperties are greater than amorphous S-EB-S gels in that they are moreresistant to cracking, tearing, crazing or rupture in flexural, tension,compression, or other deforming conditions of use. Like amorphous gels,the molded articles made from the instant composition possess theintrinsic properties of elastic memory enabling the articles to recoverand retain its original molded shape after many extreme deformationcycles.

Because of their improved tear resistance and improved resistance tofatigue, the invention gels of the present invention achieve greaterperformance than amorphous gels in low frequency vibration applications,such as viscoelastic layers in constrained-layer damping of mechanicalstructures and goods, as viscoelastic layers used in laminates forisolation of acoustical and mechanical noise, as anti-vibration elasticsupport for transporting shock sensitive loads, as vibration isolatorsfor an optical table, as viscoelastic layers used in wrappings,enclosures and linings to control sound, as compositions for use inshock and dielectric encapsulation of optical, electrical, andelectronic components.

Because of their improved tear resistance and improved resistance tofatigue, the invention gels are more useful as molded shape articles foruse in medical and sport health care, such use include therapeutic handexercising grips, dental floss, crutch cushions, cervical pillows, bedwedge pillows, leg rest, neck cushion, mattress, bed pads, elbowpadding, dermal pads, wheelchair cushions, helmet liner, cold and hotpacks, exercise weight belts, traction pads and belts, cushions forsplints, slings, and braces (for the hand, wrist, finger, forearm, knee,leg, clavicle, shoulder, foot, ankle, neck, back, rib, etc.), and alsosoles for orthopedic shoes. Other uses include various shaped articles,optical uses (e.g., cladding for cushioning optical fibers from bendingstresses) and various optical devices, as lint removers, dental floss,as tips for swabs, as fishing bait, as a high vacuum seal (againstatmosphere pressure) which contains a useful amount of a mineraloil-based magnetic fluid particles, safety airbags, medical bags, e.g.IV solution bags, blood bags and dialysis bags, etc.

The invention gels of the invention find use as airbags designed forrapid deployment by expanding pressurized or ignitable gas as describedin my pending application U.S. Ser. No. 09/130,545 which is incorporatedherein above by reference.

The various components of the airbag are denoted by: 1 Shape of gelexpansion envelop, 2 Gel, 3 External retainer, 5 internal retainer, 6reinforcing retainer, 7 mechanical retainer, 8 semi integral retainer, 9integral pin retainer, 10 partial external integral retainer, 12 body,13 gas inlet from filter, 14 outer sheet, 15 inner sheet, 16 eyeretainer ring cavity, 18, back partial integral retainer, 19 T retainer(integral reinforcing), 20 thin gel diaphram, 21 thick gel diaphragm, 22multiple progressive thinner gel diaphragm, 23 multiple progressivethicker gel diaphragm, 24 multiple single layer expansion controlelements, 25 single layer expansion control elements, 26 dual singlelayer expansion control elements, 27 multiple layer expansion controlelements, 28 multiple layer diverted elements, 29 patterned MDE, 31 fullretained gel cup, 32 partial retained gel cup, 33 gel cavity, 34 S gelshaped, 35 bulged gel, 36 compact assembly, 37 double layered, 38multiple window, 39 double gel, 40 baffle, 41 gel dia., 42 expanded7a–7d, 43 non-uniform gel dia., 44 gel restrainer, 45 restrainedenvelope, 46 non-uniform gel expanded mass, 47 expansion retainerassembly, 48 expansion control elements, 50 dual expansion dia., 52single, 54 internal and external, 56 triple, 57 multiple layered, 58triple internal, 59 triple small and dural large, 60 equal triple, 61dural internal with single external surround dia., 10c driver gel dia.,10d enveloping driver dummy, 10e enveloping passenger dummy, 11conventional air bag deployment, 12 ge and break-out pressures, 13 geldiameter expansion final pressures.

The expansion of the gel air bag is substantially pure volume expansionor dilation as related to K, bulk modulus, y, young's modulus:K=y/3(1−2t), t=3k−2n/6k−2n, where t=poisson's ratio, b=1/kcompressibility=−change in V/(V·change in pressure P).

Surface expansion measure of air bag from initial to expanded state isfrom 630 to 833% depending on thickness of original air bag. The initialair bag thickness can vary from 0.5 cm to 10 cms. (0.5, 1, 2, 3, 4, 5,6, 7, 8, 9, 10 cm and higher).

As disclosed in my pending patent application U.S. Ser. No. 10/273,828,very thin films of the gels of the invention are suitable for use asartificial muscles in the form of thin films wrapped into a cylinder.The gel film stretch when one side of a film is given a positive chargeand the other a negative. The charges cause each wrapped film tocontract toward the center of the cylinder which forces the cylinder toexpand lengthwise. When the power supply is off, the cylindrical musclesrelaxes. Thus, the roll up gel can push, pull, and lift loads.

A thin films or membrane of the gels having a thickness of about 5 mm toless than 0.1 mm are useful as artificial muscles. Film thickness offrom and in between: 0.005 mm, 0.01 mm, 0.02 mm, 0.03 mm, 0.04 mm, 0.05mm, 0.06 mm, 0.07 mm, 0.08 mm, 0.09 mm, 0.10 mm, 0.2 mm, 0.3 mm, 0.4 mm,0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, 1.2 mm, 1.3 mm,1.4 mm, 1.5 mm, 1.6 mm, 1.7 mm, 1.8 mm, 1.9 mm, 2.0 mm, 2.1 mm, 2.2 mm,2.3 mm, 2.4 mm, 2.5 mm, 2.6 mm, 2.7 mm, 2.8 mm, 2.9 mm, 3.0 mm, 3.1 mm,3.2 mm, 3.3 mm, 3.4 mm, 3.5 mm, 3.6 mm, 3.7 mm, 3.8 mm, 3.9 mm, 4.0 mmcan be utilized for forming artificial muscles of the invention.

Fine powder of the common transition metals can be utilized as a coatingelectrodes on the top and bottom flat sides of the gel film to serve asconductor, such as aluminum, alpha aluminum, copper, silver, gold, tin,nickel, iron, cobalt, zinc, lead, and the like.

We denote “|” as a gel film layer, G, and “∥” as two gel film layers,GG, side by side, “|∥” as three gel film layers, GGG, side by side. Wedenote E as a metal electrode or conductor electrode on both sides ofthe G film layer, such as EGE, EGEGE, EGEGEGE, EGEGEGEGE and the like.We denote (+) as a positive charge, (−) as a negative charge. We thendenote the single charged membrane or film layer as “(+)E|E(−)” showinga single gel layer with electrodes on both sides and a positive chargeon its left side and a negative charge on its right side. Hence“(+)E|E(−)(−)E|E(+)”, denotes a double gel thin film layers withelectrodes on each side of the film layers and charged from left toright as positive, negative, negative, and positive. This arrangementallows for the rolling up of the double layers into a cylindricalcylinder without discharging the double layers by rolling unto itself.Another way of rolling up a thin gel film “(+)E|E(−)” require foldingthe (−) side with the (−) sides as a continuous S curve layers uponlayers and then rolling the S curve so that the same charged sides rollunto itself into a cylinder. Other combination can be made for use ascharged thin film layers for artificial muscle use, such as

-   a) (+)E|E(−).-   b) (+)E|E(−)(−)E|E(+),-   c) (+)E|E(−)(−)E|E(+)(+)E|E(−),-   d) (+)E|E(−)(−)E|E(+)(+)E|E(−)(−)E|E(+), and-   e) (+)E|E(−)(−)E|E(+)(+)E|E(−)(−)E|E(+)(+)E|E(−).

Moreover, the gels films can be formed as multiple layers of films withseparating electrical conducting layer with encapsulated connectors foreasy folding.

The diameter of the rolled up gel cylinder can be from about 1 mm toabut 8 mm, suitably, about 0.5 mm to about 5 mm, more suitably about 1mm to about 3 mm. Generally the rolled up diameter can be from less than0.5 mm to about 12 mm or larger. The length of the cylinder can bealmost any suitable length, from about 5 mm to about 50 mm, suitably, 8mm to 20 mm, more suitably from less than 8 mm to 12 mm and longer.

Conductive connectors (of foil, polymer, or conductive gel) can beattached to the inner and outer electrodes respectively. The directcurrent voltage from a regulated power supply or predetermined voltagepositive or negative protental source can be applied which voltage canrange from less than 100 volts to greater than 10,000 volts. Voltages of1,000v, 2,000v, 3,000v, 4,000v, 5,000v, 6,000v, 7,000v, 8,000v, 9,000v,10,000v, 12,000v, 15,000v, 18,000v can also be used. The voltages can beregulated selectively by hand or an electronic timer from less than onethousands of a second to minutes, hours, and days duration. Electricaltiming of the applied voltages can range from a few micro seconds andlonger.

The gel film can be made by conventional extrusion, hot melt spincoating, casting, dipping and the like. The artificial muscle made inthis manner are useful as contractible muscle elements for small robotswhich gel film, contracts in thickness and extends in length and widthdue to the electrostatic forces when a voltage is applied. The gelcylinder increases and decreases in volume thickness so as to expand andcontract lengthwise due to the electrostatic forces of the charges onthe opposite dielectric surfaces of the gel film. This effect is afunction of the dielectric constant of the gel. In order to provide fora muscle with a large strain and therefore a large actuation pressure(greater than 5 MPa). The performance, efficiency and faster response ofthe cylindrical muscle depends on the amount of strain obtained underelongation. The higher strain under elongation, the better theperformance, the better the efficiency, and the faster the response.

Gel muscles actuators made from thin films having greater polyethylenecrystallinity are found to produces greater performance, greaterefficiency, and faster response than amorphous gels. This result is dueto the greater strain performance under elongation. The elongation ofthe gels of the invention can range from about 100% to greater than3,000%. The actuation pressure of the actuators made from the gels ofthe invention can range from about 5 MPa to greater than about 12 MPa.As an example, a 15 layer rolled/folded gel film actuator having aactive muscle length of 10 mm and a diameter of 3 mm (made from 0.5 mmthick SEEPS 500 gram Bloom gel) can achieve a stroke of about 3 mm and aforce of about 5 grams.

The strain under elongation of the copolymers forming the gels can rangefrom less than 8 MPa to about 18 MPa and higher as measure at a strainrate of 1000%/min., from less than 5 MPa to about 25 MPa and higher asmeasure at a strain rate of 100%/min., and from less than 5 MPa to about30 MPa and higher as measure at a strain rate of 10%/min. Reference (19)reports the fracture strain % and corresponding modulus (Mpa) forEthylene-styrene copolymers ES16, ES24, ES27, ES28, ES28, and ES30 are666/52.5, 517/26.4, 453/25, 564/19.5 and 468/25.4 respectively.

The ability to reduce the number of layers, increase strain withelongation, reduce the size of the active muscle actuator and increasethe stroke distance at a greater force can be achieved with gels(exhibiting high strain under elongation) made from copolymers havingone or more polyethylene components.

Moreover, the casted, extruded, or spun threads, strips, yarns, tapescan be weaved into cloths, fine or coarse fabrics. The forms of theinvention gel yarn can be bare, double-covered, single-covered orcoreplied, and core-spun. The invention gels can also be made intofibers such as side-side fibers, sheath-core fibers, multiple-segmentfibers, island-in-the-sea fibers, and matrix-fibril.

The weaved invention gels are of great advantage for forming orthoticsand prosthetic articles described above because such devices made fromweaved invention gels of fine to coarse fabrics will allow for the humanskin to breathe. The openings between weaved strands allows for air andoxygen transport between the skin and outer portions of the gel devicebody. Moreover, fine oriented or non-oriented invention gels (made fromSEEBS, SEEPS, E-S-E, SEEPES, SEPEEPS and the like) in the form ofthreads or yarns can be produced by extruding, spinning or forcedthrough a collection of jet nozzles to form a invention gel spray toproduce porous gel non-woven matting or webs which are skin oxygen/airbreathe-able fabrics and articles. Unlike the elastomeric nonwoven websmade at 290° C. of U.S. Pat. No. 4,692,371, the invention gels must beformed advantageously below 180° C. more advantageously at about 175° C.or lower because of the extremely high amount of plasticizer components.If the invention gels are heated to above 200° C. and higher, the resultis a puddle of hot liquid gel mass and not the porous individual formstrands forming the desired fabrics. Furthermore, the invention gels aresuperior in properties than any gels made from amorphous SEBS gels ofsubstantially corresponding rigidities.

Porous, webbing or matting that are skin breathe-able comprisinginvention gel strands can be formed into a webs or matting by coldforming sandwiched invention gels strand-s using alkyl cyanoacrylatessuch as ethyl, butyl, methyl, propyl cyanoacrylates and the like. Thealkyl cyanoacrylates (AC) will interlock with the gels of the invention,thereby resulting in gel-(AC)-gel webbing or matting articles. Alkylcyanoacrylates are useful for interlocking invention gels of theinvention with other substrates such as pottery, porcelain, wood, metal,plastics, such as acrylics, ABS, EPDM, nylon Fiberglass, phenoics,plexiglass, polycarbonate, polyesters, polystyrene, PVC, urethanes andthe like. Other cyanoacrylates such as cyanoacrylate ester are inhibitedinterlocking with the invention gels of the invention.

The invention gels can be formed in any shape; the original shape can bedeformed into another shape (to contact a regular or irregular surface)by pressure and upon removal of the applied pressure, the composition inthe deformed shape will recover back to its original shape.

As an example of the versatility of use of the invention gels, a handexerciser can be made in any shape so long as it is suitable for use asa hand exerciser: a sphere shape, a cube shape, a rectangular shape,etc. Likewise, a wheelchair cushion can be made from the composition inany shape, so long as it meets the needs of the user of the cushion. Forexample, a cushion can be made by forming the composition into aselected shape matching the contours of the specific body part or bodyregion. The composition can be formed into any desired shaped, size andthickness suitable as a cushion; the shaped composition can beadditionally surrounded with film, fabric, foam, or any other desiredmaterial or combinations thereof. Moreover, the composition can becasted onto such materials, provided such materials substantiallymaintain their integrity (shape, appearance, texture, etc.) during thecasting process. The same applies for brace cushions, liners, liningsand protective coverings for the hand, wrist, finger, forearm, knee,leg, etc.

Because of their improved tear resistance and resistance to fatigue, theinvention gels exhibit versatility as balloons for medical uses, such asballoon for valvuloplasty of the mitral valve, gastrointestinal balloondilator, esophageal balloon dilator, dilating balloon catheter use incoronary angiogram and the like.

Other uses include self sealing enclosures for splicing electrical andtelephone cables and wires. For example, the invention gels can bepre-formed into a small diameter tubing within an outer elastic tubing,both the internal invention gel tubing and external elastic tubing canbe axially expanded and fixed in place by a removable continuousretainer. Upon insertion of a spliced pair or bundle of cables or wires,the retainer can be removed, as the retainer is removed, the inventiongel and elastic tubing impinges onto the inserted cables or wiressplices, thereby sealing the electrical splices against weather, water,dirt, corrosives and shielding the splice from external abuse. Theenclosure is completed without the use of heat or flame as isconventionally performed.

Because of their improved resistance to tearing, the invention gels donot tear as readily as amorphous gels when used as dental floss. Thedental floss can be almost any shape so long as it is suitable fordental flossing. A thick shaped piece of the composition can bestretched into a thin shape and used for flossing. A thinner shapedpiece would require less stretching, etc. For purposes of dentalflossing, while flossing between two closely adjacent teeth, especiallybetween two adjacent teeth with substantial contact points and moreespecially between two adjacent teeth with substantial amalgam alloymetal contact points showing no gap between the teeth, it is criticalthat the invention gel resist tearing, shearing, and crazing while beingstretched to a high degree in such situations. For example, dentalinvention gel floss can take the form of a disk where the segments ofthe circumference of the disk is stretched for flossing between theteeth. Other shaped articles suitable for flossing include threads,strips, yarns, tapes, etc., mentioned above.

In order for invention gels to be useful as a dental floss, it mustovercome the difficult barriers of high shearing and high tearing underextreme elongation and tension loads. The difficulties that theinvention gels must overcome during flossing can be viewed as follows:during the action of flossing, the invention gel is stretched from noless than about 200% to about 1,100% or higher, the invention gel flossis deformed as it is pulled down with tearing action between thecontacting surfaces of the teeth, then, the wedge of invention gel flossis sheared between the inner contacting surfaces of the teeth, andfinally, the elongated wedged of invention gel floss is pulled upwardsand out between the surfaces of the teeth. The forces encountered in theact of flossing are: tension, shearing, tearing under extreme tension.

The use of invention gels advances the flossing art by providing strong,soft, and more tear resistant gels than amorphous gels. Floss made fromthe invention gels has many advantages over conventional dental flosssuch as regular and extra fine waxed and unwaxed nylon floss, spongynylon fiber floss, and waxed and unwaxed expanded and unexpended teflonfloss. Such conventional floss are not recommended for use by children,since a slip or sudden snap in forcing the floss between the teeth cancause injury to the gums which often times results in bleeding. Forsensitive gums and inflamed gums which has become red and puffy, it isdifficult to floss at, near, and below the gumline. The soft inventiongel floss with softness substantially matching the softness of the gumsare of great advantage for use by children and for flossing teethsurrounded by sensitive and tender gums.

In all cases, the tear strength of invention gels are higher than thatof amorphous gels. The rigidities of the invention gels for use asdental floss advantageously should be selected to exhibit a propagatingtear force (when propagating a tear as measured at 180° U bend around a5.0 mm diameter mandrel attached to a spring scale) of about 1 Kg/cm,more advantageously 2 Kg/cm, and still more advantageously of about 3Kg/cm and higher. For any gel to be considered useful for flossing, thegels should exhibit tear strengths of 2 Kg/cm and higher, advantageouslyof 4 Kg/cm and higher, more advantageously of 6 Kg/cm and higher,exceptionally more advantageously of 8 Kg/cm and higher. Typically, thetear propagation strength should range from about 5 Kg/cm to about 20Kg/cm and higher, more typically from about less than 5 Kg/cm to about25 Kg/cm and higher, especially more typically from about less than 6Kg/cm to about 30 Kg/cm and higher, and exceptionally more typicallyfrom about less than 8 Kg/cm to about 35 Kg/cm and higher.

For any gel to be considered useful for flossing, the gels, critically,should advantageously exhibit a propagating tension tear force (when acylindrical sample is notched and a tear is initiated at the notchedarea and propagated past its maximum cylindrical diameter by length-wisestretching of the cylindrical sample) of about 1 Kg/cm, moreadvantageously 2 Kg/cm, and still more advantageously of about 4 Kg/cmand higher. Although the invention gels of the present invention haveimproved tear resistance and resistance to fatigue greater than theamorphous gels at corresponding gel rigidities, the high and ultra-hightear resistant gels of my other related parent and c-i-p applicationstypically will exhibit even higher tear resistance values.

The invention gels of the invention can be use for making air bags. Theexpansion of the gel air bag is substantially pure volume expansion ordilation as related to K, bulk modulus, y, young's modulus: K=y/3(1−2t),t=3k−2n/6k−2n, where t=poisson's ratio, b=1/k compressibility=−change inV/(V*change in pressure P).

Surface expansion measure of air bag from initial to expanded state isfrom 630 to 833% depending on thickness of original air bag. The initialair bag thickness can vary from 0.5 cm to 10 cms. (0.5, 1, 2, 3, 4, 5,6, 7, 8, 9, 10 cm and higher).

While advantageous components and formulation ranges based on thedesired properties of the invention gels have been disclosed herein.Persons of skill in the art can extend these ranges using appropriatematerial according to the principles discussed herein. All suchvariations and deviations which rely on the teachings through which thepresent invention has advanced the art are considered to be within thespirit and scope of the present invention.

The invention is further illustrated by means of the followingillustrative embodiments, which are given for purpose of illustrationonly and are not meant to limit the invention to the particularcomponents and amounts disclosed.

EXAMPLE I

Gels of 100 parts of Kraton G1651, Kraton RP-6917 (amorphous S-EB-S),Septon 8006 (amorphous S-EB-S), Kraton RP-6918, Septon S2006 (amorphousS-EP-S) and a high viscosity radial amorphous midblock segment (SEB)_(n)triblock copolymers and 1,600, 1,200, 1,000, 800, 600, 500, 450, 300,250 parts by weight of Duraprime 200 white oil (plasticizer having Vis.cSt @ 40° C. of 39.0) are melt blended, test, and tack probe samplesmolded, the bulk gel rigidities are found to be within the range of 2 to1,800 gram Bloom and the tensile strength, notched tear strength, andresistance to fatigue are found to decrease with increase amounts ofplasticizers, while tackiness of the gels is found to be greater than7.6 gram Tack.

EXAMPLE II

Gels of 100 parts of Septon crystalizable (SEEPS) copolymers 4033, 4055,and 4077 and 1,600, 1,200, 1,000, 800, 600, 500, 450, 300, 250 parts byweight of Duraprime 200 white oil (plasticizer having Vis. cSt @ 40° C.of 39.0) are melt blended, test and tack probe samples molded, the bulkgel rigidities are found to be within the range of 2 to 1,800 gram Bloomand the gel tackiness are found to increase with increase amounts ofplasticizers and the tack greater than 7.6 gram Tack.

EXAMPLE III

Gels of 100 parts of Septon crystalizable (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dow S seriespoly(ethylene/styrene) random copolymer (250,000 Mw) having a highstyrene content sufficient to form gel blends with total styrene contentof 37 by weight of copolymers and 800, 600, 500, 450, 300, 250 parts byweight of Duraprime 55, 70, Klearol, Carnation, Blandol, Benol, Semtol85, 70, and 40 (plasticizers having Vis. CSt @ 40° C. of less than 20)are melt blended, tests, and tack probe samples molded, the bulk gelrigidities are found to be within the range of 2 gram to 1,800 gramBloom and the notched tear strength and resistance to fatigue of the gelat corresponding rigidities are found to be greater than that ofamorphous gels of Example I, while tack is found to decrease withdecreasing plasticizer content and in all instances substantially lowerthan the gels of Example I and II.

EXAMPLE IV

Gels of 100 parts of Septon 4045 (crystalizable S-E/EP-S having astyrene content of 37.6) and 1,600, 1,200, 1,000, 800, 600, 500, 450,300, 250 parts by weight of Duraprime Klearol white oil (plasticizerhaving Vis. CSt @ 40° C. of 7–10) are melt blended, test and probesamples molded, the bulk gel rigidities are found to be within the rangeof 2 to 2,000 gram Bloom and the tackiness is found to be less thanabout 1 gram Tack.

EXAMPLE V

Gels of 100 parts of Septon crystalizable (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of Septon 2104(Amorphous SEPS having a high styrene content of 65) and 800, 600, 500,450, 300, 250 parts by weight of Duraprime 55, 70, Klearol, Carnation,Blandol, Benol, Semtol 85, 70, and 40 (plasticizers having Vis. CSt @40° C. of less than 20) are melt blended, tests, and tack probe samplesmolded, the bulk gel rigidities are found to be within the range of 2gram to 1,800 gram Bloom and tack is found to decrease with decreasingplasticizer content and in all instances substantially lower than thegels of Example I and II.

EXAMPLE VI

Gels of 100 parts of Septon crystalizable (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dow M seriespoly(ethylene/styrene) random copolymer (350,000 Mw) having a highstyrene content sufficient to form gel blends with total styrene contentof 37 by weight of copolymers and 800, 600, 500, 450, 300, 250 parts byweight of Duraprime 55, 70, Klearol, Carnation, Blandol, Benol, Semtol85, 70, and 40 (plasticizers having Vis. CSt @ 40° C. of less than 20)are melt blended, tests, and tack probe samples molded, the bulk gelrigidities are found to be within the range of 2 gram to 1,800 gramBloom and the notched tear strength and resistance to fatigue of the gelat corresponding rigidities are found to be greater than that ofamorphous gels of Example I, while tack is found to decrease withdecreasing plasticizer content and in all instances substantially lowerthan the gels of Example I and II.

EXAMPLE VII

Gels of 100 parts of Septon crystalizable (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dow E seriespoly(ethylene/styrene) random copolymer (240,000 Mw) having a highstyrene content sufficient to form gel blends with total styrene contentof 37 by weight of copolymers and 800, 600, 500, 450, 300, 250 parts byweight of Duraprime 55, 70, Klearol, Carnation, Blandol, Benol, Semtol85, 70, and 40 (plasticizers having Vis. CSt @ 40° C. of less than 20)are melt blended, tests, and tack probe samples molded, the bulk gelrigidities are found to be within the range of 2 gram to 1,800 gramBloom and the notched tear strength and resistance to fatigue of the gelat corresponding rigidities are found to be greater than that ofamorphous gels of Example I, while tack is found to decrease withdecreasing plasticizer content and in all instances substantially lowerthan the gels of Example I and II.

EXAMPLE VIII

Gels of 100 parts of Septon crystalizable (SEEPS) copolymers 4033, 4055,and 4077 in combination with polystyrene homopolymers (having Mw of3,000; 4,000; 5,000; 6,000; 7,000; 8,000; 9,000; 10,000; 11,000; 12,000,13,000; 14,000; 15,000; 16,000; 17,000; 18,000; 19,000; 20,000; 30,000;40,000; 50,000; 60,000; 70,000; 80,000; 90,000) in sufficient amounts toform gel blends with total styrene content of 37, 45, 48, 50, and 55 byweight of copolymers and 800, 600, 500, 450, 300, 250 parts by weight ofDuraprime 55, 70, Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and40 (plasticizers having Vis. CSt @ 40° C. of less than 20) are meltblended, tests, and tack probe samples molded, the bulk gel rigiditiesare found to be within the range of 2 gram to 2,000 gram Bloom and tackis found to decrease with decreasing plasticizer content and in allinstances substantially lower than the gels of Example I and II.

EXAMPLE IX

Gels of 100 parts of Septon crystalizable (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dow M seriespoly(ethylene/styrene) random copolymer (350,000 Mw) having a highstyrene content sufficient to form gel blends with total styrenecontents of 40, 45, 48, 50, and 55 by weight of copolymers and 800, 600,500, 450, 300, 250 parts by weight of Duraprime 55, 70, Klearol,Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizers havingVis. CSt @ 40° C. of less than 20) are melt blended, tests, and tackprobe samples molded, the bulk gel rigidities are found to be within therange of 2 gram to 1,800 gram Bloom and the notched tear strength andresistance to fatigue of the gel at corresponding rigidities are foundto be greater than that of amorphous gels of Example I, while tack isfound to decrease with decreasing plasticizer content and in allinstances substantially lower than the gels of Example I and II.

EXAMPLE X

Gels of 100 parts of Septon crystalizable (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dow S seriespoly(ethylene/styrene) random copolymers (with Mw of 140,000; 250,000and 340,000) having a high styrene content sufficient to form gel blendswith total styrene content of 40, 45, 48, 50, and 55 by weight ofcopolymers and 800, 600, 500, 450, 300, 250 parts by weight of Duraprime55, 70, Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and 40(plasticizers having Vis. CSt @ 40° C. of less than 20) are meltblended, tests, and tack probe samples molded, the bulk gel rigiditiesare found to be within the range of 2 gram to 1,800 gram Bloom and thenotched tear strength and resistance to fatigue of the gel atcorresponding rigidities are found to be greater than that of amorphousgels of Example I, while tack is found to decrease with decreasingplasticizer content and in all instances substantially lower than thegels of Example I and II.

EXAMPLE XI

Gels of 100 parts of Septon crystalizable (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dow E seriespoly(ethylene/styrene) random copolymers (with Mw of 250,000; 340,000and 400,000) having a high styrene content sufficient to form gel blendswith total styrene content of 40, 45, 48, 50, and 55 by weight ofcopolymers and 800, 600, 500, 450, 300, 250 parts by weight of Duraprime55, 70, Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and 40(plasticizers having Vis. CSt@ 40° C. of less than 20) are melt blended,tests, and tack probe samples molded, the bulk gel rigidities are foundto be within the range of 2 gram to 1,800 gram Bloom and the notchedtear strength and resistance to fatigue of the gel at correspondingrigidities are found to be greater than that of amorphous gels ofExample I, while tack is found to decrease with decreasing plasticizercontent and in all instances substantially lower than the gels ofExample I and II.

EXAMPLE XII

Gels of 100 parts of Septon crystalizable (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dow M seriespoly(ethylene/styrene) random copolymer (with Mw of 250,000; 340,000 and400,000) having a high styrene content sufficient to form gel blendswith total styrene content of 40, 45, 48, 50, and 55 by weight ofcopolymers and 800, 600, 500, 450, 300, 250 parts by weight of Duraprime55, 70, Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and 40(plasticizers having Vis. CSt @ 40° C. of less than 20) are meltblended, tests, and tack probe samples molded, the bulk gel rigiditiesare found to be within the range of 2 gram to 1,800 gram Bloom and thenotched tear strength and resistance to fatigue of the gel atcorresponding rigidities are found to be greater than that of amorphousgels of Example I, while tack is found to decrease with decreasingplasticizer content and in all instances substantially lower than thegels of Example I and II.

EXAMPLE XIII

Gels of 100 parts of Dow E series crystalizable poly(ethylene/styrene)random copolymer (with Mw of 250,000; 340,000 and 400,000) having a highstyrene content sufficient to form gel blends with total styrene contentof 37, 40, 45, 48, 50, 55, and 60 by weight of copolymers and 800, 600,500, 450, 300, 250 parts by weight of Duraprime 55, 70, Klearol,Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizers havingVis. CSt @ 40° C. of less than 20) are melt blended, tests, and tackprobe samples molded, the bulk gel rigidities are found to be within therange of 2 gram to 1,800 gram Bloom and the notched tear strength andresistance to fatigue of the gel at corresponding rigidities are foundto be greater than that of amorphous gels of Example I, while tack isfound to decrease with decreasing plasticizer content and in allinstances substantially lower than the gels of Example I and II.

EXAMPLE XIV

Gels of 100 parts of Septon crystalizable (SEEPS) copolymers 4033, 4055,and 407 in combination with polystyrene (of 2,500 Mw, 4,000 Mw, 13,000Mw, 20,000 Mw, 35,000 Mw, 50,000 Mw, and 90,000 Mw;poly(alpha-methylstyrene) (of 1,300 Mw, 4,000 Mw; poly(4-methylstyrene)(of 72,000 Mw), Endex 155, 160, Kristalex 120, and 140) in sufficientamounts to form gel blends with total styrene content of 37, 45, 48, 50,and 55 by weight of copolymers and 800, 600, 500, 450, 300, 250 parts byweight of Duraprime 55, 70, Klearol, Carnation, Blandol, Benol, Semtol85, 70, and 40 (plasticizers having Vis. CSt @ 40° C. of less than 20)are melt blended, tests, and tack probe samples molded, the bulk gelrigidities are found to be within the range of 2 gram to 2,000 gramBloom and tack is found to decrease with decreasing plasticizer contentand in all instances substantially lower than the gels of Example I andII.

EXAMPLE XV

Examples XIV is repeated and gels of 100 parts of (S-EB₄₅-EP-S),(S-E-EB₂₅-S), (S-EP-E-EP-S), (S-E-EB-S), (S-E-EP-S), (S-E-EP-E-S),(S-E-EP-EB-S), (S-E-EP-E-EP-S), (S-E-EP-E-EB-S), (S-E-EP-E-EP-E-S),(S-E-EP-E-EB-S), (S-E-EP-E-EP-EB-S), and (S-E-EP-E-EP-E-S) blockcopolymers are each melt blended, tests and probe samples molded, thebulk gel rigidities are found to be within the range of 2 to 1,800 gramBloom and tack is found to decrease with decreasing plasticizer contentand in all instances substantially lower than the gels of Example I andII.

EXAMPLE XVI

Example XIV is repeated and minor amounts of 2, 5, 10 and 15 parts ofthe following polymers are formulated with each of the triblockcopolymers: styrene-butadiene-styrene block copolymers,styrene-isoprene-styrene block copolymers, low viscositystyrene-ethylene-butylene-styrene block copolymers,styrene-ethylene-propylene block copolymers,styrene-ethylene-propylene-styrene block copolymers, styrene-butadiene,styrene-isoprene, polyethyleneoxide, poly(dimethylphenylene oxide),polystyrene, polybutylene, polyethylene, polypropylene, high ethylenecontent EPDM, amorphous copolymers based on2,2-bistrifluoromethyl-4,5-difuoro-1,3-dioxole/tetrafluoroethylene. Thebulk gel rigidities of each of the formulations are found to be withinthe range of 2 gram to 2,000 gram Bloom and tack is found to decreasewith decreasing plasticizer content and in all instances substantiallylower than the gels of Example I and II.

EXAMPLE XVII

Molten gels of Examples III–XVI are formed into s with paper, foam,plastic, elastomers, fabric, metal, concrete, wood, glass, ceramics,synthetic resin, synthetic fibers, and refractory materials and theresistance to fatigue of the invention gels at corresponding rigiditiesare found to be greater than that of the amorphous gels of Example I.

EXAMPLE XVIII

Three cm thick sheets of each of the invention gels of Example XIV andthe amorphous gels of Example I are tested by repeatedly displacing thesheets to a depth of 1 cm using a 10 cm diameter smooth (water soaked)wood plunger for 1,000, 5,000, 10,000, 25,000, 50,000, and 100,000cycles. The sheets of invention gels are found capable of exhibitinggreater fatigue resistance than the sheets of amorphous gels atcorresponding rigidities.

EXAMPLE XIX

Gels of 100 parts of Septon crystalizable (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES16 having 37.5% crystallinityand 800, 600, 500, 450, 300, 250 parts by weight of Duraprime 55, 70,Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizershaving Vis. CSt @ 40° C. of less than 20) are melt blended, tests, andtack probe samples molded, the bulk gel rigidities are found to bewithin the range of 2 gram to 1,800 gram Bloom and the notched tearstrength and resistance to fatigue of the gel at correspondingrigidities are found to be greater than that of amorphous gels ofExample I.

EXAMPLE XX

Gels of 100 parts of Septon crystalizable (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES24 having 26.6% crystallinityand 800, 600, 500, 450, 300, 250 parts by weight of Duraprime 55, 70,Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizershaving Vis. CSt @ 40° C. of less than 20) are melt blended, tests, andtack probe samples molded, the bulk gel rigidities are found to bewithin the range of 2 gram to 1,800 gram Bloom and the notched tearstrength and resistance to fatigue of the gel at correspondingrigidities are found to be greater than that of amorphous gels ofExample I.

EXAMPLE XXI

Gels of 100 parts of Septon crystalizable (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES27 having 17.4% crystallinityand 800, 600, 500, 450, 300, 250 parts by weight of Duraprime 55, 70,Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizershaving Vis. CSt @ 40° C. of less than 20) are melt blended, tests, andtack probe samples molded, the bulk gel rigidities are found to bewithin the range of 2 gram to 1,800 gram Bloom and the notched tearstrength and resistance to fatigue of the gel at correspondingrigidities are found to be greater than that of amorphous gels ofExample I.

EXAMPLE XXII

Gels of 100 parts of Septon crystalizable (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES28 having 22.9% crystallinityand 800, 600, 500, 450, 300, 250 parts by weight of Duraprime 55, 70,Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizershaving Vis. CSt @ 40° C. of less than 20) are melt blended, tests, andtack probe samples molded, the bulk gel rigidities are found to bewithin the range of 2 gram to 1,800 gram Bloom and the notched tearstrength and resistance to fatigue of the gel at correspondingrigidities are found to be greater than that of amorphous gels ofExample I.

EXAMPLE XXIII

Gels of 100 parts of Septon crystalizable (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES30 having 19.6% crystallinityand 800, 600, 500, 450, 300, 250 parts by weight of Duraprime 55, 70,Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizershaving Vis. CSt @ 40° C. of less than 20) are melt blended, tests, andtack probe samples molded, the bulk gel rigidities are found to bewithin the range of 2 gram to 1,800 gram Bloom and the notched tearstrength and resistance to fatigue of the gel at correspondingrigidities are found to be greater than that of amorphous gels ofExample I.

EXAMPLE XXIV

Gels of 100 parts of Septon crystalizable (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES44 having 5.0% crystallinityand 800, 600, 500, 450, 300, 250 parts by weight of Duraprime 55, 70,Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizershaving Vis. CSt @ 40° C. of less than 20) are melt blended, tests, andtack probe samples molded, the bulk gel rigidities are found to bewithin the range of 2 gram to 1,800 gram Bloom and the notched tearstrength and resistance to fatigue of the gel at correspondingrigidities are found to be greater than that of amorphous gels ofExample I.

EXAMPLE XXV

Gels of 100 parts of Septon crystalizable (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES72 and 800, 600, 500, 450,300, 250 parts by weight of Duraprime 55, 70, Klearol, Carnation,Blandol, Benol, Semtol 85, 70, and 40 (plasticizers having Vis. CSt @40° C. of less than 20) are melt blended, tests, and tack probe samplesmolded, the bulk gel rigidities are found to be within the range of 2gram to 1,800 gram Bloom and the notched tear strength and resistance tofatigue of the gel at corresponding rigidities are found to be greaterthan that of amorphous gels of Example I.

EXAMPLE XXVI

Gels of 100 parts of Septon crystalizable (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES73 and 800, 600, 500, 450,300, 250 parts by weight of Duraprime 55, 70, Klearol, Carnation,Blandol, Benol, Semtol 85, 70, and 40 (plasticizers having Vis. CSt @40° C. of less than 20) are melt blended, tests, and tack probe samplesmolded, the bulk gel rigidities are found to be within the range of 2gram to 1,800 gram Bloom and the notched tear strength and resistance tofatigue of the gel at corresponding rigidities are found to be greaterthan that of amorphous gels of Example I.

EXAMPLE XXVII

Gels of 100 parts of Septon crystalizable (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES74 and 800, 600, 500, 450,300, 250 parts by weight of Duraprime 55, 70, Klearol, Carnation,Blandol, Benol, Semtol 85, 70, and 40 (plasticizers having Vis. CSt @40° C. of less than 20) are melt blended, tests, and tack probe samplesmolded, the bulk gel rigidities are found to be within the range of 2gram to 1,800 gram Bloom and the notched tear strength and resistance tofatigue of the gel at corresponding rigidities are found to be greaterthan that of amorphous gels of Example I.

EXAMPLE XXVIII

Gels of 100 parts of Septon crystalizable (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES69 and 800, 600, 500, 450,300, 250 parts by weight of Duraprime 55, 70, Klearol, Carnation,Blandol, Benol, Semtol 85, 70, and 40 (plasticizers having Vis. CSt @40° C. of less than 20) are melt blended, tests, and tack probe samplesmolded, the bulk gel rigidities are found to be within the range of 2gram to 1,800 gram Bloom and the notched tear strength and resistance tofatigue of the gel at corresponding rigidities are found to be greaterthan that of amorphous gels of Example I.

EXAMPLE XXIX

Gels of 100 parts of Septon crystalizable (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES62 and 800, 600, 500, 450,300, 250 parts by weight of Duraprime 55, 70, Klearol, Carnation,Blandol, Benol, Semtol 85, 70, and 40 (plasticizers having Vis. CSt @40° C. of less than 20) are melt blended, tests, and tack probe samplesmolded, the bulk gel rigidities are found to be within the range of 2gram to 1,800 gram Bloom and the notched tear strength and resistance tofatigue of the gel at corresponding rigidities are found to be greaterthan that of amorphous gels of Example I.

EXAMPLE XXX

Gels of 100 pats of Septon (SEPS) copolymers Kraton GRP6918 incombination with each of a Dow poly(ethylene/styrene) random copolymersES16, ES24, ES27, ES28, ES30, and ES44 and 800, 600, 500, 450, 300, 250parts by weight of Duraprime 55, 70, Klearol, Carnation, Blandol, Benol,Semtol 85, 70, and 40 (plasticizers having Vis. CSt @ 40° C. of lessthan 20) are melt blended, tests, and tack probe samples molded, thebulk gel rigidities are found to be within the range of 2 gram to 1,800gram Bloom and the notched tear strength and resistance to fatigue ofthe gel at corresponding rigidities are found to be greater than that ofamorphous gels of Example I.

EXAMPLE XXXI

Gels of 100 parts of Septon (SEBS) copolymers S8006 and Kraton G1651,G1654 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES16, ES24, ES27, ES28, ES30,and ES44 and 800, 600, 500, 450, 300, 250 parts by weight of Duraprime55, 70, Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and 40(plasticizers having Vis. CSt @ 40° C. of less than 20) are melt bleed,tests, and tack probe samples molded, the bulk gel rigidities are foundto be within the range of 2 gram to 1,800 gram Bloom and the notchedtear strength and resistance to fatigue of the gel at correspondingrigidities are found to be greater than that of amorphous gels ofExample I.

EXAMPLE XXXII

Gels of 100 parts of Septon (SEEPS) copolymers 4033, 4045, 4055, 4077 incombination each with 25 pats by weight of Super Sta-tac, BetapreneNevtac, Escorez, Hercotac, Wingtack, Piccotac, polyterpene, Zonarez,Nirez, Piccolyte, Sylvatac, glycerol ester of rosin (Foral),pentaerythritol ester of rosin (Pentalyn), saturated alicyclichydrocarbon (Arkon P), coumarone indene (Cumar LX), hydrocarbon (Picco6000. Regalrez), mixed olefin (Wingtack), alkylated aromatic hydrocarbon(Nevchem), Polyalphamethylstyrene/vinyl toluene copolymer (Piccotex),polystyrene (Kristalex, Piccolastic), special resin (LX-1035) and 800,600, 500, 450, 300, 250 parts by weight of Duraprime 55, 70, Klearol,Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizers havingVis. CSt @ 40° C. of less than 20) are melt blended, tests, and tackprobe samples molded, the bulk gel rigidities are found to be within therange of 2 gram to 1,800 gram Bloom and the notched tear strength andresistance to fatigue of the gel at corresponding rigidities are foundto be greater than that of amorphous gels of Example I.

EXAMPLE XXXIII

Gels of 100 parts of Septon (SEEPS) copolymers 4033, 4045, 4055, 4077 incombination each with 25 parts by weight of Super Sta-tac, BetapreneNevtac, Escorez, Hercotac, Wingtack, Piccotac, polyterpene, Zonarez,Nirez, Piccolyte, Sylvatac, glycerol ester of rosin (Foral),pentaerythritol ester of rosin (Pentalyn), saturated alicyclichydrocarbon (Arkon P), coumarone indene (Cumar LX), hydrocarbon (Picco6000, Regalrez), mixed olefin (Wingtack), alkylated aromatic hydrocarbon(Nevchem), Polyalphamethylstyrene/vinyl toluene copolymer (Piccotex),polystyrene (Kristalex, Piccolastic), special resin (LX-1035) and 800,600, 500, 450, 300, 250 parts by weight of Duraprime 55, 70, Klearol,Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizers havingVis. CSt @ 40° C. of less than 20) are melt blended, tests, and tackprobe samples molded, the bulk gel rigidities are found to be within therange of 2 gram to 1,800 gram Bloom and the notched tear strength andresistance to fatigue of the gel at corresponding rigidities are foundto be greater than that of amorphous gels of Example I.

While preferred components and formulation ranges have been disclosedherein persons of skill in the art can extend these ranges usingappropriate material according to the principles discussed herein.Furthermore, Crystalizable midblock segment block polymers can be use inblending with other engineering plastics and elastomeric polymers tomake alloyed compositions having improved impact and tear resistanceproperties. All such variations and deviations which rely on theteachings through which the present invention has advanced the art areconsidered to be within the spirit and scope of the present invention.

1. An adherent gel comprising from (a) 100 parts by weight of one or amixture of two or more of a hydrogenated styrene isoprene/butadienestyrene block copolymer(s); (b) from about 300 to about 1,600 parts byweight of one or more of a plasticizing oil(s), and a minor amount ofone or more resin(s) to aid in adhesion; wherein said adherent gelhaving greater tear resistance than a corresponding gel ofstyrene-ethylene-propylene-styrene block copolymer.
 2. An adherent gelof claim 1, wherein said copolymer is one or more of a hydrogenatedstyrene block copolymer(s) with 2-methyl-1,3-butadiene and 1,3-butadieneof the configuration poly(styrene-ethylene-ethylene-propylene-styrene).3. An adherent gel of claim 1, wherein said composition is characterizedby a gel rigidity of from about 2 gram to about 1,800 gram Bloom.
 4. Anadherent gel composite comprising (a) 100 parts by weight of one or morepoly(styrene-ethylene-ethylene-propylene-styrene) block copolymers; (b)from about 300 to about 1,600 parts by weight of a plasticizing oil; (c)a selected minor amount of one or more resin(s) to aid in adhesion; saidblock copolymers being in combination with or without one or morelinear, multi-arm, branched, or star shaped copolymer of the generalconfiguration poly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-propylene-styrene),poly(styrene-ethylene-butylene)n, poly(styrene-ethylene-propylene)n or amixture thereof and in combination with or without a selected amount ofat least one polymer or copolymer selected from the group consisting ofpoly(styrene-butadiene-styrene), poly(styrene-butadiene),poly(styrene-isoprene-styrene), poly(styrene-isoprene),poly(styrene-ethylene-propylene), low viscositypoly(styrene-ethylene-propylene-styrene), low viscositypoly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-butylene), polystyrene, polybutylene,poly(ethylene-propylene)n, poly(ethylene-butylene)n, polypropylene, andpolyethylene, wherein said selected copolymer is a linear, branched,multiarm, or star shaped copolymer and said subscript n is 2 or greater;said composite wherein said gel being denoted by G, is physicallyinterlocked with a selected material M forming a composite of thecombination G_(n)G_(n), G_(n)M_(n), G_(n)M_(n)G_(n), M_(n)G_(n)M_(n),M_(n)G_(n)G_(n), M_(n)M_(n)G_(n), M_(n)M_(n)M_(n)G_(n),M_(n)M_(n)M_(n)G_(n)M_(n), M_(n)G_(n)G_(n)M_(n), G_(n)M_(n)G_(n)G_(n),G_(n)M_(n)M_(n)G_(n), G_(n)G_(n)M_(n)M_(n), G_(n)G_(n)M_(n)G_(n)M_(n),G_(n)M_(n)G_(n)M_(n)M_(n), M_(n)G_(n)M_(n)G_(n)M_(n)G_(n),G_(n)G_(n)M_(n)M_(n)G_(n), G_(n)G_(n)M_(n)G_(n)M_(n)G_(n), or apermutation of one or more of said G_(n) with M_(n), wherein when n is asubscript of M, n is the same or different selected from the groupconsisting of foam, plastic, fabric, metal, concrete, wood, wire screen,refractory material, glass, synthetic resin, and synthetic fibers; andwherein when n is a subscript of G, n denotes the same or a differentgel rigidity of from about 2 gram to about 1,800 gram Bloom, saidcomposite gels of two or more G_(n) having one or more of the same or adifferent resin(s) for adhesion; wherein said adherent gel havinggreater tear and greater fatigue resistance than a corresponding gel ofstyrene-ethylene-propylene-styrene block copolymer alone.
 5. An adherentgel comprising from (a) 100 parts by weight of one or more highviscosity block copolymer; (b) from about 300 to about 1,600 parts byweight of one or more of a plasticizing oil, and a minor amount of twoor more of an adhesion resins; wherein said adherent gel having greatertear resistance than a corresponding gel ofstyrene-ethylene-propylene-styrene block copolymer.
 6. An adherent gelcomprising from (a) 100 parts by weight of one or morepoly(styrene-ethylene-ethylene-propylene-styrene) block copolymer; (b)from about 300 to about 1,600 parts by weight of one or more of aselected plasticizing oil(s), and a selected amount of one or more of anadhesion resin(s), said block copolymer having a Viscosity of aviscosity at 5 weight percent solution in toluene at 30° C. of about 90mPa-S, at 10 weight percent about 5800 mPa-S; said adhesion resinselected from the group consisting of polymerized mixed olefins,polyterpene, glycerol ester of rosin, pentaerythritol ester of rosin,saturated alicyclic hydrocarbon, coumarone indene, hydrocarbon, mixedolefin, alkylated aromatic hydrocarbon, Polyalphamethylstyrene/vinyltoluene copolymer, and polystyrene; wherein said adherent gel havinggreater tear resistance than a corresponding gel ofstyrene-ethylene-propylene-styrene block copolymer.
 7. An adherent gelcomprising from (a) 100 parts by weight of one or morepoly(styrene-ethylene-ethylene-propylene-styrene) block copolymers incombination with or without one or more multi-armpoly(styrene-ethylene-propylene)_(n) block copolymers, said n being anumber 2 or greater; (b) from about 300 to about 1,600 parts by weightof one or more of a selected plasticizing oil(s), and a selected amountof one or more of an adhesion resin; wherein said adherent gel havinggreater tear and greater fatigue resistance than a corresponding gel ofstyrene-ethylene-propylene-styrene block copolymer.
 8. An adherent gelcomprising from (a) 100 parts by weight of one or morepoly(styrene-ethylene-ethylene-propylene-styrene) block copolymer; (b)from about 300 to about 1,600 parts by weight of one or more of aselected plasticizing oil, and a selected amount of one or more of anadhesion resin(s); wherein said adherent gel having greater tearresistance than a corresponding gel ofstyrene-ethylene-propylene-styrene block copolymer.
 9. An adherent gelcomprising from (a) 100 parts by weight of one or morepoly(styrene-ethylene-ethylene-propylene-styrene) block copolymer, (b)from about 300 to about 1,600 parts by weight of one or more of aplasticizing oil, and a selected amount of one or more of an adhesionresin(s), said block copolymer in combination with or without a minoramount of one or more linear, multi-arm, branched, or star shapedcopolymer of the general configurationpoly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-propylene)_(n),poly(styrene-ethylene-butylene)_(n),poly(styrene-ethylene-ethylene-propylene-styrene), or a mixture thereofand in combination with or without a selected amount of one or morepolymer or copolymer of poly(styrene-butadiene-styrene),poly(styrene-butadiene), poly(styrene-isoprene-styrene),poly(styrene-isoprene), poly(styrene-ethylene-propylene)_(n), lowviscosity poly(styrene-ethylene-propylene-styrene), low viscositypoly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-butylene)_(n), low viscositypoly(styrene-ethylene-ethylene-propylene-styrene), polystyrene,polybutylene, poly(ethylene-propylene), poly(ethylene-butylene),polypropylene, or polyethylene, wherein said selected copolymer is alinear, branched, multiarm, or star shaped copolymer; said n being anumber 2 or greater.
 10. An adherent gel composite comprising (I) 100parts by weight of one or morepoly(styrene-ethylene-ethylene-propylene-styrene) block copolymers; (II)from about 300 to about 1,600 parts by weight of a plasticizing oil;(III) a selected amount of one or more of an adhesion resin(s); and incombination with or without a minor amount of one or more a linear,multi-arm, branched, or star shaped copolymer of the generalconfiguration poly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-propylene)n, poly(styrene-ethylene-butylene)n,poly(styrene-ethylene-ethylene-propylene-styrene), or a mixture thereofand in combination with or without a selected amount of one or morepolymer or copolymer of poly(styrene-butadiene-styrene),poly(styrene-butadiene), poly(styrene-isoprene-styrene),poly(styrene-isoprene), poly(styrene-ethylene-propylene)n, low viscositypoly(styrene-ethylene-propylene-styrene), low viscositypoly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-butylene)n, low viscositypoly(styrene-ethylene-ethylene-propylene-styrene), polystyrene,polybutylene, poly(ethylene-propylene), poly(ethylene-butylene),polypropylene, or polyethylene, wherein said selected copolymer is alinear, branched, multiarm, or star shaped copolymer, said n being anumber 2 or greater; said composite wherein said gel being denoted by G,is physically interlocked with a selected material M forming a compositeof the combination G_(n)G_(n, G) _(n)M_(n), G_(n)M_(n)G_(n),M_(n)G_(n)M_(n), M_(n)G_(n)G_(n), M_(n)M_(n)G_(n), M_(n)M_(n)M_(n)G_(n),M_(n)M_(n)M_(n)G_(n)M_(n), M_(n)G_(n)G_(n)M_(n), G_(n)M_(n)G_(n)G_(n),G_(n)M_(n)M_(n)G_(n), G_(n)G_(n)M_(n)M_(n), G_(n)G_(n)M_(n)G_(n)M_(n),G_(n)M_(n)G_(n)M_(n)M_(n), M_(n)G_(n)M_(n)G_(n)M_(n)G_(n),G_(n)G_(n)M_(n)M_(n)G_(n), G_(n)G_(n)M_(n)G_(n)M_(n)G_(n), or apermutation of one or more of said G_(n) with M_(n), wherein when n is asubscript of M, n is the same or different selected from the groupconsisting of foam, plastic, fabric, metal, concrete, wood, wire screen,refractory material, glass, synthetic resin, and synthetic fibers; andwherein when n is a subscript of G, n denotes the same or a differentgel rigidity of from about 2 gram to about 1,800 gram Bloom, saidcomposite gels of two or more G_(n) with or without M_(n) having one ormore of the same or a different resin(s) for adhesion; wherein saidadherent gel having greater tear resistance than a corresponding gel ofstyrene-ethylene-propylene-styrene block copolymer.
 11. An adherent gelaccording to claim 1 for dermal use.
 12. An adherent gel according toclaim 1, wherein said block copolymers ispoly(styrene-ethylene-ethylene-propylene-styrene).